CN102596570B

CN102596570B - Multi-layer structure

Info

Publication number: CN102596570B
Application number: CN201080049341.8A
Authority: CN
Inventors: 川边雅之; 涩谷光夫; 井上馨; 酒井纪人
Original assignee: Nippon Synthetic Chemical Industry Co Ltd
Current assignee: Mitsubishi Kasei Corp
Priority date: 2009-08-31
Filing date: 2010-08-18
Publication date: 2015-03-04
Anticipated expiration: 2030-08-18
Also published as: CN102596570A; EP2474415A1; EP2474415A4; EP2474415B1; WO2011024686A1; US20120156513A1

Abstract

Provided is a multi-layer structure comprising the following layers: a layer (A) consisting primarily of a polyethylene terephthalate resin, which comprises a dicarboxylic acid component that contains terephthalic acid and a diol component that consists primarily of ethylene glycol, wherein the copolymer fraction of non-terephthalic-acid dicarboxylic acids in the dicarboxylic acid component is 15-40 mol% of the entire dicarboxylic acid component; and a layer (B) that is adjacent to the abovementioned layer (A) and consists primarily of a polyvinyl alcohol resin having the structural unit represented by general formula (1). This results in increased interlayer adhesion between the layers (A and B), yielding a multi-layer structure that is highly resistant to separation of the layers thereof. (1) (In formula (1), R1, R2, and R3 each independently represent a hydrogen atom or an organic group, and X represents a single bond or a bond chain. R4, R5, and R6 each independently represent a hydrogen atom or an organic group.)

Description

Multilayer structure making

Technical field

The present invention relates to the layer that has using PET series resin as main component and using polyvinyl alcohol resin as the layer of main component and the multilayer structure making of the adhesiveness between layers excellence of these layers.

Background technology

Usually, the excellence such as the transparency, barrier of polyvinyl alcohol resin, effectively utilizes such characteristic, and is configured as film or sheet material etc., thus can be used in various packaging material.And then, for the container such as bottle of gas barrier property requiring height, be used in the container of the sandwich construction between PET series resin with polyvinyl alcohol resin layer all the time.

The container of sandwich construction as described above is obtained by polyvinyl alcohol resin and melt extruding altogether of PET series resin.

But, above-mentioned polyvinyl alcohol resin due to fusing point and decomposition point close, so such as obtaining molding by melt-shaping time, because of the generation etc. of foreign matter, coking, cause the aesthetic appearance of obtained molding poor, therefore, in order to address these problems, such as proposing by the degree of polymerization 200 ~ 1200, saponification degree 75 ~ 99.99 % by mole and the terminal carboxyl group of fusing point 160 ~ 230 DEG C and the total amount of end lactonic ring is the melt-shaping polyvinyl alcohol resin composition (with reference to patent document 1) that the polyvinyl alcohol of 0.008 ~ 0.15 % by mole and alkali metal salt form.

But with regard to polyvinyl alcohol resin composition disclosed in above-mentioned patent document 1, the fusing point of fully saponified thing is still about 200 ~ 230 DEG C, and fusing point is high, insufficient for solving the problem.Therefore, in order to solve such problem, proposition is used in the polyvinyl alcohol resin (with reference to patent document 2) that side chain contains 1, the 2-diol bond of 2 ~ 10 % by mole.

Prior art document

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2000-178396 publication

Patent document 2: Japanese Unexamined Patent Publication 2004-75866 publication

Summary of the invention

the problem that invention will solve

In above-mentioned patent document 2, really can in the situation decline low melting point of not plasticizer-containing, even if the good molding of outward appearance also can be obtained under the melt-shaping temperature conditions of relatively low temperature.But in the molding obtained by melt extruding the polyester based resin of above-mentioned polyvinyl alcohol resin and its two sides, there is room for improvement in adhesiveness between layers, the peel resistance about interlayer is expected to improve further.

The present invention carries out in view of such situation, its object is to the multilayer structure making of the adhesiveness between layers excellence providing PET series resin and polyvinyl alcohol resin.

for the scheme of dealing with problems

In order to reach above-mentioned purpose, multilayer structure making of the present invention takes following formation: it is the multilayer structure making with the Rotating fields that layer (A) is laminated with layer (B), described layer (A) is containing by having PET series resin that dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component formed as main component, described layer (B) adjoins with above-mentioned layer (A), and containing there is the polyvinyl alcohol resin of the construction unit shown in following general formula (1) as main component, above-mentioned layer (A) possesses any one in following manner (x) ~ (z) with the relation of layer (B).

[chemical formula 1]

(in above-mentioned formula (1), R ¹, R ²and R ³separately represent hydrogen atom or organic group, X represents singly-bound or bonding chain.R ⁴, R ⁵and R ⁶separately represent hydrogen atom or organic group.〕

(x) layer (A) to be formed and the copolymerization ratios of dicarboxylic acids beyond terephthalic acid (TPA) in above-mentioned dicarboxylic acid component is the layer of PET series resin as main component of 15 ~ 40 % by mole of whole dicarboxylic acid component containing by having dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component, and layer (B) is the layer of polyvinyl alcohol resin as main component containing having the construction unit shown in above-mentioned general formula (1).

(y) layer (A) is containing by having dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component is formed, and the copolymerization ratios of dicarboxylic acids beyond terephthalic acid (TPA) in above-mentioned dicarboxylic acid component is more than 2 % by mole of whole dicarboxylic acid component and lower than the PET series resin of 15 % by mole as the layer of main component, layer (B) be there is the construction unit shown in above-mentioned general formula (1) polyvinyl alcohol resin as main component, also containing the layer relative to the entire infrastructure unit of above-mentioned polyvinyl alcohol resin being at least one in the alkali metal salt of 0.03 ~ 1 % by mole and alkali salt.

(z) layer (A) to be formed and end carboxy concentration is the layer of PET series resin as main component of the scope of 15 ~ 60 equivalents/ton containing by having dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component, and above-mentioned layer (B) is the layer of polyvinyl alcohol resin as main component containing having the construction unit shown in above-mentioned general formula (1).

That is, wait in view of the foregoing, the present inventor, in order to improve the adhesiveness between layers of PET series resin bed and polyvinyl alcohol resin layer, has carried out a series of research.In its process, remember that the shrinkage factor making both is close, reduce the difference of its shrinkage factor, repeatedly study further based on this idea.And, found out by this research, as using terephthalic acid (TPA) as dicarboxylic acid component, and using ethylene glycol as the PET series resin of the main component of glycol component, dicarboxylic acid component beyond use terephthalic acid (TPA) is as above-mentioned dicarboxylic acid component, use the polyvinyl alcohol resin with the construction unit shown in aforementioned formula (1) on the other hand, thus make the crystallinity of PET series resin and polyvinyl alcohol resin all mixed and disorderly and reduce, not easily produce contraction thus, the difference of two-layer shrinkage factor can be reduced, result is, the raising of adhesiveness between layers can be sought.

But, the dicarboxylic acids beyond above-mentioned terephthalic acid (TPA) is only used to be inadequate, centered by the compounding amount of the dicarboxylic acid component thus beyond (x) this terephthalic acid (TPA) or for the copolymerization ratios of the dicarboxylic acid component beyond (y) this terephthalic acid (TPA) and the formation material of the layer that uses above-mentioned polyvinyl alcohol resin to be formed or the above-mentioned PET series resin (z) to the carboxyl becoming reactive group, conduct in-depth research respectively.It found that, by using the dicarboxylic acids (mode (x)) beyond above-mentioned terephthalic acid (TPA) with the scope of 15 ~ 40 % by mole in whole dicarboxylic acid component; Or in whole dicarboxylic acid component, the dicarboxylic acids beyond terephthalic acid (TPA) is used with more than 2 % by mole and lower than the scope of 15 % by mole, and pass through in above-mentioned polyvinyl alcohol resin with at least one in the compounding use alkali metal salt of the scope of 0.03 ~ 1 % by mole and alkali salt, thus play catalytic action in the esterification of the carboxyl of above-mentioned slaine in PET series resin and the hydroxyl in polyvinyl alcohol resin, so both reactivities improve (mode (y)); Or by the PET series resin that the end carboxy concentration in use PET series resin is the high concentration of the scope of 15 ~ 60 equivalents/ton, thus the reaction site in PET series resin becomes many, so generate ester bond (mode (z)) at the hydroxyl of its carboxyl of two-layer interface and polyvinyl alcohol resin, the adhesiveness between layers that can obtain above-mentioned PET series resin bed and polyvinyl alcohol resin layer improves, the multilayer structure making of peel resistance excellence, thus completes the present invention.

the effect of invention

Like this, the present invention is a kind of multilayer structure making, it is the multilayer structure making with the Rotating fields that layer (A) is laminated with layer (B), described layer (A) is containing by having PET series resin that dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component formed as main component, described layer (B) adjoins with above-mentioned layer (A), and containing there is the polyvinyl alcohol resin of the construction unit shown in general formula described later (1) as main component, above-mentioned layer (A) possesses any one in above-mentioned mode (x) ~ (z) with the relation of layer (B).Therefore, the crystallinity of above-mentioned PET series resin and above-mentioned polyvinyl alcohol resin reduces, the layer (A) using it to be formed and layer (B) not easily shrink, not easily cause splitting because shrinking difference thus, the peel resistance with the multilayer structure making of this Rotating fields becomes excellent, and adhesiveness between layers improves.

And, in above-mentioned mode (x), in layer (B) using polyvinyl alcohol resin as main component, containing when being at least one in the alkali metal salt of 0.001 ~ 1 % by mole and alkali salt relative to the entire infrastructure unit of polyvinyl alcohol resin, the multilayer structure making that peel resistance is excellent further can be obtained.

In addition, in above-mentioned mode (z), above-mentioned PET series resin, when to have terephthalic acid (TPA) be the PET series resin of 2 ~ 40 % by mole of whole dicarboxylic acid component as dicarboxylic acid component, the copolymerization ratios of dicarboxylic acids that has beyond the terephthalic acid (TPA) of ethylene glycol as the main component of glycol component and in above-mentioned dicarboxylic acid component, further can be improved the effect of adhesiveness between layers.

And then, in above-mentioned mode (z), in layer (B) using polyvinyl alcohol resin as main component, containing when being at least one in the alkali metal salt of 0.001 ~ 1 % by mole and alkali salt relative to the entire infrastructure unit of polyvinyl alcohol resin, catalytic action is played, so the more excellent multilayer structure making of peel resistance can be obtained in the esterification that this slaine occurs at two-layer interface.

And, in above-mentioned mode (x) ~ (z), when the dicarboxylic acids beyond above-mentioned terephthalic acid (TPA) is M-phthalic acid, further can be improved the effect of adhesiveness between layers.

Detailed description of the invention

Then, embodiments of the present invention are described in detail.But the present invention is not limited to this embodiment.

Multilayer structure making of the present invention is the multilayer structure making that layer (A) is laminated with layer (B), described layer (A) is that resin is as main component containing specific PETG (below sometimes referred to as " PET "), described layer (B) and this layer (A) adjoin, and are that resin is as main component containing the polyvinyl alcohol (below sometimes referred to as " PVA ") with specific construction unit.In addition, in the present invention, so-called main component refers to and accounts for overall more than half composition, and it is intended to also comprise overall situation about being only made up of main component.In addition, as long as the adjacent structure with at least above-mentioned 2 Rotating fields of multilayer structure making of the present invention, structure, shape that other layers etc. make other also can be set.

And the feature of multilayer structure making of the present invention is, based on the relation of adjacent above-mentioned layer (A) with layer (B), possess any one in following shown mode (x) ~ (z).

(x) layer (A) to be formed and the copolymerization ratios of dicarboxylic acids beyond terephthalic acid (TPA) in above-mentioned dicarboxylic acid component is the layer of PET series resin as main component of 15 ~ 40 % by mole of whole dicarboxylic acid component containing by having dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component, and layer (B) is the layer of polyvinyl alcohol resin as main component containing having the construction unit shown in following general formula (1).

(y) layer (A) is containing by having dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component is formed, and the copolymerization ratios of dicarboxylic acids beyond terephthalic acid (TPA) in above-mentioned dicarboxylic acid component is more than 2 % by mole of whole dicarboxylic acid component and lower than the PET series resin of 15 % by mole as the layer of main component, layer (B) be there is the construction unit shown in following general formula (1) polyvinyl alcohol resin as main component, also containing the layer relative to the entire infrastructure unit of above-mentioned polyvinyl alcohol resin being at least one in the alkali metal salt of 0.03 ~ 1 % by mole and alkali salt.

(z) layer (A) to be formed and end carboxy concentration is the layer of PET series resin as main component of the scope of 15 ~ 60 equivalents/ton containing by having dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component, and above-mentioned layer (B) is the layer of polyvinyl alcohol resin as main component containing having the construction unit shown in following general formula (1).

[chemical formula 2]

(1) " multilayer structure making in mode (x) "

Below, carry out describing to the multilayer structure making in mode (x).

First, be described containing the layer (A) of specific PET system resin as main component.

< contains layer (A) > of specific PET system resin as main component

Layer (A) in mode (x) by using containing the formation material of specific PET system resin as main component, and carries out such as melt-shaping to it and obtains.

The feature of above-mentioned specific PET system resin is, it is dicarboxylic acid component by being made up of the dicarboxylic acids beyond terephthalic acid (TPA) and terephthalic acid (TPA) and the condensation polymer obtained as the polycondensation reaction of the glycol component of main component using ethylene glycol, and the copolymerization ratios of dicarboxylic acids beyond terephthalic acid (TPA) in above-mentioned dicarboxylic acid component is set in the scope of 15 ~ 40 % by mole of whole dicarboxylic acid component.Preferably, the copolymerization ratios of the dicarboxylic acids beyond the terephthalic acid (TPA) in above-mentioned dicarboxylic acid component is the scope of 15 ~ 30 % by mole of whole dicarboxylic acid component, is particularly preferably the scope of 20 ~ 30 % by mole.If the copolymerization ratios of the dicarboxylic acids beyond above-mentioned scope and beyond terephthalic acid (TPA) is very few, then can not get the raising effect of the adhesiveness between layers brought because making the crystallinity of PET system resin mixed and disorderly, if the copolymerization ratios of the dicarboxylic acids beyond terephthalic acid (TPA) is too much, be then difficult to form the layer (A) using specific PET system resin as main component.

As the dicarboxylic acids beyond the terephthalic acid (TPA) in above-mentioned dicarboxylic acid component, include, for example out M-phthalic acid, diphenyl-4, 4 '-dicarboxylic acids, diphenoxyethanedicarboxylic acid, 2, 6-naphthalene dicarboxylic acids, 2, aromatic dicarboxylic acid and their the ester formative derivatives such as 7-naphthalene dicarboxylic acids, adipic acid, decanedioic acid, azelaic acid, the aliphatic dicarboxylic acids such as butanedioic acid and their ester formative derivative, cyclohexane dicarboxylic acid, alicyclic dicarboxylic acid and their the ester formative derivatives such as six hydrogen terephthalic acid (TPA)s, P-hydroxybenzoic acid, the carboxylic acids such as hydroxycaproic acid and their ester formative derivative, and trimellitic acid, PMA etc.They can be used alone, or combine two or more use.Wherein, when considering processability, intensity, cost etc., preferably M-phthalic acid is used.

As above-mentioned glycol component, spent glycol can be made as main component, glycol component can be only made up of this ethylene glycol, in addition, also such as diethylene glycol, 1 can be used together with ethylene glycol, ammediol, 1, the aliphatic diols such as 4-butanediol, neopentyl glycol, 1, the alicyclic diols such as 4-cyclohexanedimethanol, the aromatic diols such as the alkylene oxide addition product of bisphenol-A, bisphenol-A, the PAGs such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and glycerine, 1,3-PD, pentaerythrite etc.They can be used alone, or combine two or more use.In addition, diethylene glycol generates owing to being reacted by by-product when the manufacture of ethylene glycol, so usually contain a small amount of diethylene glycol in ethylene glycol.As above-mentioned glycol component, from the view point of heat resistance, be preferably only made up of ethylene glycol except a small amount of by-product diethylene glycol.

Above-mentioned specific PET system resin manufactures basically by by using terephthalic acid (TPA) as the dicarboxylic acid component of main component and the usual manufacture method of mylar that obtains using ethylene glycol as the glycol component of main component.

Namely, have: carry out esterification as the dicarboxylic acid component of main component with using ethylene glycol as the glycol component of main component at esterification groove by using terephthalic acid (TPA), obtained esterification reaction product is transferred to the direct polymerization method of carrying out polycondensation in polycondensation reaction groove; By using the ester formative derivative of terephthalic acid (TPA) as the dicarboxylic acid component of main component with carry out ester exchange reaction using ethylene glycol as the glycol component of main component at ester exchange reaction groove, obtained product of transesterification reaction is transferred to the ester-interchange method carrying out polycondensation in polycondensation reaction groove.These reactions can be carried out with batch (-type), also can carry out with continous way.In addition, the dicarboxylic acid component beyond terephthalic acid (TPA) can add in the arbitrary moment before esterification or ester exchange reaction terminate, but operationally preferred to add with the form of the slurry formed with ethylene glycol.

In addition, usually, the resin obtained by polycondensation reaction is extracted out from the outlet port of the bottom being arranged on polycondensation reaction groove with strand form, while water-cooled or after water-cooled, cuts off and make graininess with cutting machine.Then, make its solid phase by heating the particle after this polycondensation, thus the higher degree of polymerization can be obtained, and the acetaldehyde, low molecule oligomer etc. as byproduct of reaction can be reduced.

In addition, in previous building methods, esterification such as uses the esterification catalyst such as acylate, alkoxide of antimony oxide or antimony, titanium, magnesium, calcium etc. as required, in the temperature of about 200 ~ 270 DEG C, 1 × 10 ⁵~ 4 × 10 ⁵carry out under the pressure of about Pa; Ester exchange reaction such as uses the ester exchange catalysts such as the acylate of lithium, sodium, potassium, magnesium, calcium, manganese, titanium, zinc etc. as required, in the temperature of about 200 ~ 270 DEG C, 1 × 10 ⁵~ 4 × 10 ⁵carry out under the pressure of about Pa.

In addition, polycondensation reaction such as uses the phosphorus compounds such as orthophosphoric acid, phosphorous acid and their ester as stabilizing agent, such as use the polycondensation catalysts such as the acylate of the metal oxide such as antimony oxide, germanium dioxide, four germanium oxides or antimony, germanium, zinc, titanium, cobalt, alkaline-earth metal etc., alkoxide, in the temperature of about 240 ~ 290 DEG C, 1 × 10 ²~ 2 × 10 ³carry out under the decompression of about Pa.

In addition, above-mentioned specific PET system resin also can carry out solid phase after aforesaid polycondensation reaction, by heating 1 minute with first-class and carry out Pre-crystallizing at the temperature of about 120 ~ 200 DEG C, then under the atmosphere of the not active gases such as temperature, nitrogen of 180 ~ fusing point about-5 DEG C or/and 1 × 10 ²~ 2 × 10 ³carry out under the decompression of about Pa.

The inherent viscosity of above-mentioned specific PET system resin is preferably more than 0.60dl/g and the scope of below 1.20dl/g.By making the inherent viscosity of above-mentioned specific PET system resin in this scope, the multilayer structure making that can obtain intensity He have excellent formability.That is, when the inherent viscosity of PET system resin is less than 0.60dl/g, intensity reduces, and during more than 1.20dl/g, formability reduces.

And the inherent viscosity of above-mentioned specific PET system resin is more preferably more than 0.60dl/g and the scope of below 1.00dl/g.

Formed in material containing above-mentioned specific PET system resin as the layer (A) of main component, except above-mentioned specific PET system resin, can also the suitable additive such as compounding such as pigment dispersing agent, thickener, flow ability modifying agent (flow modifier), surfactant, defoamer, releasing agent, bleeding agent, dyestuff, pigment, fluorescent whitening agent, ultra-violet absorber, antioxidant, anticorrisive agent, mould inhibitor as required.

As the method for compounding of each composition, include, for example out the method for use cylinder (tumbler) cylinder (tumbler), Henschel mixer etc., be supplied to the method etc. carrying out in extruder loading hopper mixing by dispenser quantitatively.As compounding process, the method using single screw extrusion machine, double screw extruder etc. can be listed.

Then, be described containing the characteristic of above-mentioned specific PET system resin as the layer (A) of main component.

< contains the characteristic > of specific PET system resin as the layer (A) of main component

The thickness of above-mentioned layer (A) is not particularly limited, and is usually preferably 0.1 ~ 800 μm, is particularly preferably 0.1 ~ 500 μm, more preferably 0.1 ~ 300 μm.This is because, when the thickness of layer (A) is blocked up, the tendency that the flexibility seeing multilayer structure making reduces, on the contrary, when thickness is crossed thin, intensity difference, sees and is difficult to keep the tendency as the shape of various formed body.

Then, be described containing the layer (B) of PVA system resin as main component.

< contains layer (B) > of PVA system resin as main component

In mode (x) containing PVA system resin as the layer (B) of main component by using using the formation material of specific PVA system resin as main component with the construction unit shown in following general formula (1), and such as melt-shaping is carried out to it and obtains.

[chemical formula 3]

The feature of above-mentioned specific PVA system resin is, as mentioned above, has the construction unit shown in general formula (1), i.e. 1,2-dihydroxylic alcohols construction unit.Structure division beyond it is same with common PVA system resin, and be made up of vinyl alcohol construction unit and vinyl acetate construction unit, its ratio suitably can adjust according to the degree of saponification.

First, the construction unit shown in above-mentioned general formula (1) is described.In 1,2-dihydroxylic alcohols construction unit shown in above-mentioned general formula (1), the R in formula (1) ¹~ R ³and R ⁴~ R ⁶for hydrogen atom or any monovalent organic radical, they can be mutually the same, also can be different.Wherein, R ¹~ R ³and R ⁴~ R ⁶when being all hydrogen atom, be preferred from the aspect of the copolyreaction of the monomer of fabrication stage and industrial treatability.But, as long as damaging in the scope of resin properties not significantly, R ¹~ R ³and R ⁴~ R ⁶also can be organic group at least partially.As above-mentioned organic group, be not particularly limited, the alkyl of the carbon numbers 1 ~ 4 such as such as preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, and then also can have the substituting groups such as halogen radical, hydroxyl, ester group, carboxylic acid group, sulfonic group as required.

In addition, shown in above-mentioned general formula (1) 1, in 2-dihydroxylic alcohols construction unit, from the aspect of excellent heat stability, the aspect not making the crystallinity of PVA excessively reduce, the aspect etc. that do not hinder melt fluidity, the preferred singly-bound of X in formula (1).Here, X is that singly-bound refers to that X is certainly as key.

In addition, as long as in the scope not hindering effect of the present invention, above-mentioned X also can be various bonding chain.As above-mentioned bonding chain, such as, except the alkyl such as alkylidene, alkylene group, alkynylene, phenylene, naphthylene (these alkyl also can by replacements such as halogen such as fluorine, chlorine, bromines) ,-O-,-(CH also can be listed ₂o) _m-,-(OCH ₂) _m-,-(CH ₂o) _mcH ₂-,-CO-,-COCO-,-CO (CH ₂) _mcO-,-CO (C ₆h ₄) CO-,-S-,-CS-,-SO-,-SO ₂-,-NR-,-CONR-,-NRCO-,-CSNR-,-NRCS-,-NRNR-,-HPO ₄-,-Si (OR) ₂-,-OSi (OR) ₂-,-OSi (OR) ₂o-,-Ti (OR) ₂-,-OTi (OR) ₂-,-OTi (OR) ₂o-,-Al (OR)-,-OAl (OR)-,-OAl (OR) O-etc.

In above-mentioned each bonding chain, R is arbitrary substituting group, include, for example out hydrogen atom, alkyl, they can mutually the same also can be different, repeat number m is natural number in addition.And, in above-mentioned bonding chain, from the aspect of stability when manufacturing or when using, the alkylidene ,-CH of preferred carbon number less than 6 ₂oCH ₂-.

Therefore, in mode (x), in above-mentioned specific PVA system resin, particularly preferably use and there is the PVA system resin of 1,2-dihydroxylic alcohols construction unit shown in following formula (1a) as 1,2-dihydroxylic alcohols construction unit shown in above-mentioned general formula (1).

[chemical formula 4]

The method for making of the above-mentioned specific PVA system resin used in mode (x) can by such as (α) by vinyl acetate and 3, 4-bis-acyloxy-1-butylene particularly 3, the method of the copolymer saponification of 4-diacetoxy-1-butylene, (β) by vinyl acetate and the copolymer saponification of vinylethylene carbonate and the method for decarbonate, (γ) by vinyl acetate and 2, 2-dialkyl group-4-vinyl-1, the copolymer saponification of 3-dioxolanes and de-ketalization method, (δ) manufacture methods such as the method for the copolymer saponification of vinyl acetate and allylin are manufactured.Wherein, carry out well from polymerization, the characteristic of advantage when easily 1,2-dihydroxylic alcohols construction unit being imported equably the medium manufacture of resin of PVA system and final PVA system resin sets out, preferably adopt above-mentioned manufacture method (α).

The average degree of polymerization of the specific PVA system resin obtained like this (measuring according to JISK6726) is preferably 250 ~ 2000 usually, is particularly preferably 300 ~ 1000, and more preferably 300 ~ 600.That is, when average degree of polymerization is too low, the intensity seeing PVA resin becomes insufficient tendency.On the contrary, time too high, such as in utilizing the layer of melt-shaping to be formed, mobility is low, sees the tendency of the layer of the thickness be difficult to desired by formation.

In addition, the saponification degree of specific PVA system resin is preferably 80 ~ 100 % by mole usually, is particularly preferably 85 ~ 99.9 % by mole, more preferably 88 ~ 99.9 % by mole.That is, when saponification degree is too low, sees longtime running long-time stable maneuverability such as () melt-shapings and reduce, or produce the smelly tendency of acetic acid.Saponification degree in the present invention represents with the rate of change (% by mole) to conversion of hydroxyl such as ester moiety of vinyl esters system monomer.

The saponification of above-mentioned specific PVA system resin such as can as described belowly be carried out.Usually, after in PVA system resin dissolves to alcohol series solvent, under the existence of base catalyst or acid catalyst, carry out saponification.

As alcohol series solvent, such as, can use the mixed solvent etc. of the various alcohol such as the mixed solvent of methyl alcohol, ethanol, butanols, isopropyl alcohol or methyl alcohol and methyl acetate and methyl acetate.The concentration of the PVA system resin in alcohol series solvent is preferably selected from the scope of 10 ~ 60 % by weight.

As above-mentioned base catalyst, such as, can use the alkali-metal hydroxide such as NaOH, potassium hydroxide, sodium methoxide, caustic alcohol, potassium methoxide or the such base catalyst of alkoxide.As acid catalyst, such as, can use the organic acids such as the inorganic acid aqueous solution such as hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid.The use amount of base catalyst is preferably 1 ~ 100 mM relative to the vinyl acetate construction unit in PVA system resin 1 mole, is particularly preferably 1 ~ 40 mM, more preferably 1 ~ 20 mM.When the use amount of base catalyst is very few, exists and be difficult to tendency saponification degree being increased to target saponification degree, on the contrary, when the use amount of base catalyst is too much, exists and become too high tendency compared with target saponification degree, be difficult to control, thus not preferred.In addition, the temperature such as usual preferably 10 ~ 70 DEG C during saponification is carried out, more preferably 20 ~ 50 DEG C.

And then, as importing 1 in specific PVA system resin, 2-dihydroxylic alcohols bonded amount, i.e. 1 shown in aforementioned formula (1), the content (modification degree) of 2-dihydroxylic alcohols construction unit, such as usually be preferably 0.1 ~ 12 % by mole, be particularly preferably 1 ~ 10 % by mole, more preferably 3 ~ 8 % by mole.That is, when content (modification degree) is very few, fusing point uprises, and sees the tendency that formability reduces.In addition, when content (modification degree) is too much, the degree of polymerization is difficult to improve during fabrication, sees the tendency that productivity ratio reduces.

Above-mentioned specific PVA system resin can be used alone, and in the scope not hindering various characteristic, particularly heat fusing formability, also can combinationally use other PVA system resin.

As other PVA system resins above-mentioned, include, for example out the alpha-olefin modified PVA system resins such as unmodified PVA system resin (degree of polymerization 300 ~ 500, saponification degree more than 80 % by mole), carboxyl acid modified PVA system resin, ethylidene ether modification PVA system resin, amide modifications PVA system resin, vinyl ethers modified PVA system resin, ethene, vinyl esters modified PVA system resin, amine modified PVA system resin, oxyalkylene modified PVA system resin etc.They can be suitably compounding as required, and such as preferred is 0 ~ 40 % by weight relative to PVA system resin entirety.

In addition, mode (x) is preferably described above, material is formed as layer (B), use using the formation material of specific PVA system resin as main component with the construction unit shown in above-mentioned general formula (1), specifically, above-mentioned specific PVA system resin account for that layer (B) forms material monolithic more than 50 % by weight.

Further, from aspects such as the raisings of the raising of adhesiveness between layers, melt-shaping, material is formed as layer (B), at least one in preferred compounding alkali metal salt and alkali salt.As above-mentioned alkali metal salt, include, for example out the organic acid slaines such as the acetic acid of potassium, sodium etc., propionic acid, butyric acid, laurate, stearic acid, 12-hydroxy stearic acid, oleic acid, behenic acid, the slaine of the inorganic acid such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid of potassium, sodium etc.In addition, as above-mentioned alkali salt, include, for example out the organic acid slaines such as the acetic acid of calcium, magnesium etc., propionic acid, butyric acid, laurate, stearic acid, oleic acid, behenic acid, the slaine of the inorganic acid such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid of calcium, magnesium etc.They can be used alone or combine two or more and use.Wherein, from the aspect of the size of the effect relative to compounding amount, preferably, as alkali metal salt, be used alone or in combination sodium acetate, as alkali salt, be used alone or in combination magnesium acetate.

As the compounding amount of at least one in above-mentioned alkali metal salt and alkali salt, usually being preferably set to relative to the entire infrastructure unit of PVA system resin is 0.001 ~ 1 % by mole, particularly preferably be set to 0.002 ~ 0.8 % by mole, be preferably set to 0.01 ~ 0.5 % by mole further.That is, when above-mentioned slaine is very few, be difficult to the further raising effect obtaining adhesiveness between layers, contrary too much time, see resin and occur painted or make the tendency of the deteriorated appearance of multilayer structure making because of the foaming caused by thermal decomposition.

And then, layer (B) is formed in material can suitable compounding other compositions except above-mentioned specific PVA system resin and slaine as required, as other compositions, aliphatic polybasic alcohols and the ethylene oxide adducts thereof such as such as glycerine, ethylene glycol, hexylene glycol can be listed, the plasticizer such as glycitols such as D-sorbite, mannitol, pentaerythrite; The representative examples of saturated aliphatic such as stearmide, ethylene bis stearamide amide compound, the unsaturated aliphatic amide compounds such as oleamide, the aliphatic metal salt such as calcium stearate, dolomol, zinc stearate, molecular weight is the low molecular weight polyethylene of about 500 ~ 10000, the lubriation materials such as low-molecular-weight polyolefin such as low-molecular-weight polypropylene; And the inorganic acid such as boric acid, phosphoric acid; Antioxidant; Heat stabilizer; Light stabilizer; Ultra-violet absorber; Colouring agent; Antistatic additive; Surfactant; Anticorrisive agent; Antiseptic; Antiblocking agent; Slip agent; Filler etc.

Above-mentioned layer (B) forms that material is such as described below to be obtained.That is, by compounding various composition and obtaining as required wherein after modulation above-mentioned specific PVA system resin.

Then, be described containing the characteristic of above-mentioned PVA system resin as the layer (B) of main component.

< contains the characteristic > of PVA system resin as the layer (B) of main component

Containing above-mentioned PVA system resin as the layer (B) of main component thickness be usually preferably 0.1 ~ 500 μm, be particularly preferably 0.3 ~ 300 μm, more preferably 0.5 ~ 100 μm.That is, when the thickness of layer (B) is blocked up, the rigidity of multilayer structure making becomes too high and lacks flexibility, sees the tendency reduced the patience of impacting, on the contrary, when thickness is crossed thin, sees the tendency that cannot play sufficient barrier property.

(2) " multilayer structure making in mode (y) "

Then, carry out describing to the multilayer structure making in mode (y).

< contains layer (A) > of specific PET system resin as main component

Layer (A) in mode (y) by use containing specific PET system resin as main component formation material and such as melt-shaping is carried out to it and obtains.

One of feature of above-mentioned specific PET system resin is, its be the dicarboxylic acid component with terephthalic acid (TPA) with using ethylene glycol as the condensation polymer of the glycol component of main component, the copolymerization ratios of the dicarboxylic acids beyond the terephthalic acid (TPA) in above-mentioned dicarboxylic acid component is set as more than 2 % by mole of whole dicarboxylic acid component and lower than the scope of 15 % by mole.The copolymerization ratios of the dicarboxylic acids beyond the terephthalic acid (TPA) in preferred above-mentioned dicarboxylic acid component is the scope of 2 ~ 12 % by mole of whole dicarboxylic acid component, particularly preferably the scope of 5 ~ 12 % by mole.When the copolymerization ratios of the dicarboxylic acids beyond above-mentioned scope and beyond terephthalic acid (TPA) is very few, can not get because the crystallinity of PET system resin produces the raising effect of the adhesiveness between layers brought in a jumble; When the copolymerization ratios of the dicarboxylic acids beyond terephthalic acid (TPA) is too much, be difficult to form the layer (A) using specific PET system resin as main component.

As above-mentioned glycol component, spent glycol can be made as main component, glycol component can be only made up of this ethylene glycol, in addition, also such as diethylene glycol, 1 can be used together with ethylene glycol, ammediol, 1, the aliphatic diols such as 4-butanediol, neopentyl glycol, 1, the alicyclic diols such as 4-cyclohexanedimethanol, the aromatic diols such as the alkylene oxide addition product of bisphenol-A, bisphenol-A, the PAGs such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and glycerine, 1,3-PD, pentaerythrite etc.They can be used alone, or combine two or more use.In addition, diethylene glycol generates owing to being reacted by by-product when the manufacture of ethylene glycol, so usually contain a small amount of diethylene glycol in ethylene glycol.As above-mentioned glycol component, from the view point of heat resistance, preferably except a small amount of by-product diethylene glycol, only form glycol component by ethylene glycol.

Namely, have: in esterification groove, carry out esterification as the dicarboxylic acid component of main component with using ethylene glycol as the glycol component of main component by using terephthalic acid (TPA), obtained esterification reaction product is transferred to the direct polymerization method of carrying out polycondensation in polycondensation reaction groove; By using the ester formative derivative of terephthalic acid (TPA) as the dicarboxylic acid component of main component with carry out ester exchange reaction using ethylene glycol as the glycol component of main component in ester exchange reaction groove, obtained product of transesterification reaction is transferred to the ester-interchange method carrying out polycondensation in polycondensation reaction groove.These reactions can be carried out also can carrying out with continous way with batch (-type).In addition, the dicarboxylic acid component beyond terephthalic acid (TPA) can add in the arbitrary moment before esterification or ester exchange reaction terminate, but the upper preferred form with the slurry formed with ethylene glycol of operation is added.

In addition, usually, the resin obtained by polycondensation reaction is extracted out from the outlet port of the bottom being arranged on polycondensation reaction groove with strand form, while water-cooled or after water-cooled, cuts off and make graininess with cutting machine.Then, carrying out solid phase by heating the particle after this polycondensation, the higher degree of polymerization can be obtained, and the acetaldehyde, low molecule oligomer etc. of byproduct of reaction can be reduced.

In addition, polycondensation reaction such as uses the phosphorus compounds such as orthophosphoric acid, phosphorous acid and their ester as stabilizing agent, use the metal oxides such as such as antimony oxide, germanium dioxide, four germanium oxides, or the polycondensation catalysts such as the acylate of antimony, germanium, zinc, titanium, cobalt, alkaline-earth metal etc., alkoxide, in the temperature of about 240 ~ 290 DEG C, 1 × 10 ²~ 2 × 10 ³carry out under the decompression of about Pa.

In addition, solid phase is carried out in the aforesaid polycondensation reaction that also can continue of above-mentioned specific PET system resin, by heating 1 minute with first-class and carry out Pre-crystallizing at the temperature of about 120 ~ 200 DEG C, then under the atmosphere of the not active gases such as temperature, nitrogen of 180 ~ fusing point about-5 DEG C or/and 1 × 10 ²~ 2 × 10 ³carry out under the decompression of about Pa.

Formed in material containing above-mentioned specific PET system resin as the layer (A) of main component, except above-mentioned specific PET system resin, can also the suitable additive such as compounding such as pigment dispersing agent, thickener, flow ability modifying agent, surfactant, defoamer, releasing agent, bleeding agent, dyestuff, pigment, fluorescent whitening agent, ultra-violet absorber, antioxidant, anticorrisive agent, mould inhibitor as required.

As the method for compounding of each composition, include, for example out the method for use cylinder (tumbler), Henschel mixer etc., be supplied to the method etc. carrying out in extruder loading hopper mixing by dispenser quantitatively.As compounding process, the method using single screw extrusion machine, double screw extruder etc. can be listed.

The thickness of above-mentioned layer (A) is not particularly limited, and is usually preferably 0.1 ~ 800 μm, is particularly preferably 0.1 ~ 500 μm, more preferably 0.1 ~ 300 μm.When the thickness of layer (A) is blocked up, the tendency that the flexibility seeing multilayer structure making reduces, on the contrary, when thickness is crossed thin, intensity difference, sees and is difficult to keep the tendency as the shape of various formed body.

< contains layer (B) > of PVA system resin as main component

Passing through to use using the specific PVA system resin with the construction unit shown in following general formula (1) as main component containing the layer (B) of PVA system resin as main component and wherein containing the formation material of at least one in alkali metal salt and alkali salt with specific ratio in mode (y), and such as melt-shaping is carried out to it and obtains.

[chemical formula 5]

First, the construction unit shown in above-mentioned general formula (1) is described.In 1,2-dihydroxylic alcohols construction unit shown in above-mentioned general formula (1), with in mode (x) before describe same, the R in formula (1) ¹~ R ³and R ⁴~ R ⁶for the organic group of hydrogen atom or monovalence, they can be mutually the same, also can be different.Wherein, R ¹~ R ³and R ⁴~ R ⁶when being all hydrogen atom, be preferred from the aspect of the copolyreaction of the monomer of fabrication stage and industrial treatability.But, as long as damaging in the scope of resin properties not significantly, R ¹~ R ³and R ⁴~ R ⁶also can be organic group at least partially.As above-mentioned organic group, be not particularly limited, the alkyl of the carbon numbers 1 ~ 4 such as such as preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, also can have the substituting groups such as halogen radical, hydroxyl, ester group, carboxylic acid group, sulfonic group as required further.

In addition, shown in above-mentioned general formula (1) 1, in 2-dihydroxylic alcohols construction unit, from the aspect of excellent heat stability, the aspect not making the crystallinity of PVA excessively reduce, the aspect etc. that do not hinder melt fluidity, the preferred singly-bound of X in formula (1).Wherein X is that singly-bound refers to that X is certainly as key.

In above-mentioned each bonding chain, R is arbitrary substituting group, include, for example out hydrogen atom, alkyl, they can mutually the same also can be different, repeat number m is natural number in addition.Further, in above-mentioned bonding chain, from the aspect of stability when manufacturing or when using, the alkylidene ,-CH of preferred carbon number less than 6 ₂oCH ₂-.

Therefore, in mode (y), in above-mentioned specific PVA system resin, same with mode (x), particularly preferably use and there is the PVA system resin of 1,2-dihydroxylic alcohols construction unit shown in following formula (1a) as 1,2-dihydroxylic alcohols construction unit shown in above-mentioned general formula (1).

[chemical formula 6]

The method for making of the above-mentioned specific PVA system resin used in mode (y) is same with mode (x), such as can by (α) by vinyl acetate and 3, 4-bis-acyloxy-1-butylene particularly 3, the method of the copolymer saponification of 4-diacetoxy-1-butylene, (β) by vinyl acetate and the copolymer saponification of vinylethylene carbonate and the method for decarbonate, (γ) by vinyl acetate and 2, 2-dialkyl group-4-vinyl-1, the copolymer saponification of 3-dioxolanes and de-ketalization method, (δ) manufacture methods such as the method for the copolymer saponification of vinyl acetate and allylin are manufactured.Wherein, carry out well from polymerization, the characteristic of advantage when easily 1,2-dihydroxylic alcohols construction unit being imported equably the medium manufacture of resin of PVA system and final PVA system resin sets out, preferably adopt above-mentioned manufacture method (α).

The average degree of polymerization of the specific PVA system resin obtained like this (measuring according to JISK6726) is preferably 200 ~ 2000 usually, is particularly preferably 250 ~ 1000, and more preferably 300 ~ 600.That is, when average degree of polymerization is too low, the tendency that PVA resin becomes fragile is seen.On the contrary, time too high, such as in utilizing the layer of melt-shaping to be formed, mobility is low, sees the tendency of the layer of the thickness be difficult to desired by formation.

In addition, the saponification degree of specific PVA system resin is preferably 80 ~ 100 % by mole usually, is particularly preferably 85 ~ 99.9 % by mole, more preferably 88 ~ 99.9 % by mole.That is, when saponification degree is too low, sees longtime running (maneuverability steady in a long-term such as melt-shaping) and reduce or produce the smelly tendency of acetic acid.Saponification degree in the present invention represents with the rate of change (% by mole) to conversion of hydroxyl such as ester moiety of vinyl esters system monomer.

As alcohol series solvent, such as, can use the mixed solvent etc. of the various alcohol such as the mixed solvent of methyl alcohol, ethanol, butanols, isopropyl alcohol, methyl alcohol and methyl acetate and methyl acetate.The concentration of the PVA system resin in alcohol series solvent is preferably selected from the scope of 10 ~ 60 % by weight.

As above-mentioned base catalyst, such as, can use the base catalyst that the alkali-metal hydroxide such as NaOH, potassium hydroxide, sodium methoxide, caustic alcohol, potassium methoxide, alkoxide are such.As acid catalyst, such as, can use the inorganic acid aqueous solution such as hydrochloric acid, sulfuric acid, the organic acids such as p-methyl benzenesulfonic acid.The use amount of base catalyst is preferably 1 ~ 100 mM relative to the vinyl acetate construction unit in PVA system resin 1 mole, is particularly preferably 1 ~ 40 mM, more preferably 1 ~ 20 mM.When the use amount of base catalyst is very few, exists and be difficult to tendency saponification degree being increased to target saponification degree, on the contrary, when the use amount of base catalyst is too much, exists and become too high tendency compared with target saponification degree, be difficult to control, thus not preferred.In addition, the temperature such as usual preferably 10 ~ 70 DEG C during saponification is carried out, more preferably 20 ~ 50 DEG C.

Form the PVA system resin used in material as layer (B), can be used alone above-mentioned specific PVA system resin, but in the scope not hindering various characteristic, particularly heat fusing formability, also can combinationally use other PVA system resin.

As other PVA system resin above-mentioned, include, for example out the alpha-olefin modified PVA system resins such as unmodified PVA system resin (degree of polymerization 300 ~ 500, saponification degree more than 80 % by mole), carboxyl acid modified PVA system resin, ethylidene ether modification PVA system resin, amide modifications PVA system resin, vinyl ethers modified PVA system resin, ethene, vinyl esters modified PVA system resin, amine modified PVA system resin, oxyalkylene modified PVA system resin etc.They can be suitably compounding as required, and such as preferred is 0 ~ 40 % by weight relative to PVA system resin entirety.

And, in mode (y), form material as layer (B), together with the specific PVA system resin with the construction unit shown in above-mentioned general formula (1), alkali metal salt, alkali salt individually or can be combinationally used.These slaines play catalytic action to the esterification of the hydroxyl in the carboxyl in the dicarboxylic acid component in above-mentioned PET resin and above-mentioned specific PVA system resin as previously mentioned.

As above-mentioned alkali metal salt, include, for example out the organic acid slaines such as the acetic acid of potassium, sodium etc., propionic acid, butyric acid, laurate, stearic acid, oleic acid, behenic acid, the slaine of the inorganic acid such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid of potassium, sodium etc.In addition, as above-mentioned alkali salt, include, for example out the organic acid slaines such as the acetic acid of calcium, magnesium etc., propionic acid, butyric acid, laurate, stearic acid, 12-hydroxy stearic acid, oleic acid, behenic acid, the slaine of the inorganic acid such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid of calcium, magnesium etc.They can be used alone or combine two or more and use.Wherein, from the aspect of the size of effect corresponding to compounding amount, preferably, as alkali metal salt, be used alone or in combination sodium acetate, as alkali salt, be used alone or in combination magnesium acetate, dolomol.

As the compounding amount of at least one in above-mentioned alkali metal salt and alkali salt, usually being preferably set to relative to the entire infrastructure unit of PVA system resin is 0.03 ~ 1 % by mole, is particularly preferably set to 0.05 ~ 0.8 % by mole, is preferably set to 0.08 ~ 0.5 % by mole further.That is, when above-mentioned slaine is very few, be difficult to the further raising effect obtaining adhesiveness between layers, contrary too much time, see resin and occur painted or make the tendency of the deteriorated appearance of multilayer structure making because of the foaming caused by thermal decomposition.

And then, being formed in material at layer (B) can suitable compounding other composition except above-mentioned specific PVA system resin and slaine as required, as other compositions, aliphatic polybasic alcohols and the ethylene oxide adducts thereof such as such as glycerine, ethylene glycol, hexylene glycol can be listed, the plasticizer such as glycitols such as D-sorbite, mannitol, pentaerythrite; The representative examples of saturated aliphatic such as stearmide, ethylene bis stearamide amide compound, the unsaturated aliphatic amide compounds such as oleamide, the aliphatic metal salt such as calcium stearate, dolomol, zinc stearate, molecular weight is the lubriation materials such as low-molecular-weight polyolefin such as low molecular weight polyethylene, low-molecular-weight polypropylene of about 500 ~ 10000; And the inorganic acid such as boric acid, phosphoric acid; Antioxidant; Heat stabilizer; Light stabilizer; Ultra-violet absorber; Colouring agent; Antistatic additive; Surfactant; Anticorrisive agent; Antiseptic; Antiblocking agent; Slip agent; Filler etc.

Containing above-mentioned PVA system resin as the layer (B) of main component thickness be usually preferably 0.1 ~ 500 μm, be particularly preferably 0.3 ~ 300 μm, more preferably 0.5 ~ 100 μm.That is, this is because, when the thickness of layer (B) is blocked up, the rigidity of multilayer structure making becomes too high and lacks flexibility, sees the tendency reduced the patience of impacting, on the contrary, when thickness is crossed thin, sees the tendency that cannot play sufficient barrier property.

(3) " multilayer structure making in mode (z) "

Then, carry out describing to the multilayer structure making in mode (z).

< contains layer (A) > of specific PET system resin as main component

Layer (A) in mode (z) by use containing specific PET resin as main component formation material and such as melt-shaping is carried out to it and obtains.

The feature of above-mentioned specific PET system resin is, its be the dicarboxylic acid component with terephthalic acid (TPA) with using ethylene glycol as the condensation product of the glycol component of main component, and end carboxy concentration is the scope of 15 ~ 60 equivalents/ton.Preferred end carboxy concentration is 18 ~ 50 equivalents/ton, is particularly preferably 20 ~ 40 equivalents/ton.Namely, end carboxy concentration beyond above-mentioned scope and too low time, the carboxyl becoming so-called reaction site is very few, can not get the raising effect of the sufficient cementability of two interlayers brought by the esterification with the hydroxyl in PVA system described later resin, during opposite ends carboxyl excessive concentration, easily cause hydrolysis, molecular weight reduces, and the intensity of the multilayer structure making obtained reduces.

In addition, above-mentioned end carboxyl concentration (AV) such as can as described belowly measure.That is, make specific PET system resin samples be dissolved into after in solvent, carry out acid-base titration with aqueous slkali.As blank, do not use PET system resin samples and implement same operation, being calculated by following formula.

AV (equivalent/ton)=(A-B) × 0.1 × f/W

(wherein, the amount (μ L) of the aqueous slkali of A needed for titration, the amount (μ L) of the aqueous slkali of B needed for blank titration, W is the amount (g) of PET system resin samples, and f is the titer of aqueous slkali.〕

Specific PET system resin is like this such as by the dicarboxylic acid component that is made up of the dicarboxylic acids beyond terephthalic acid (TPA) and terephthalic acid (TPA) with obtain using ethylene glycol as the polycondensation reaction of the glycol component of main component.

The copolymerization ratios of the dicarboxylic acids beyond the terephthalic acid (TPA) in above-mentioned dicarboxylic acid component is preferably set to the scope of 0 ~ 40 % by mole of whole dicarboxylic acid component.More preferably the scope of 2 ~ 40 % by mole, the particularly preferably scope of 12 ~ 40 % by mole.When the copolymerization ratios of the dicarboxylic acids beyond terephthalic acid (TPA) is very few, be difficult to obtain because the crystallinity of PET resin produces the sufficient raising effect of the adhesiveness between layers brought in a jumble, when the copolymerization ratios of the dicarboxylic acids beyond terephthalic acid (TPA) is too much, the heat resistance seeing specific PET system resin reduces or is difficult to the tendency of the layer (A) formed using specific PET system resin as main component.

As above-mentioned glycol component, spent glycol can be made as main component, glycol component can be only made up of this ethylene glycol, in addition, also such as diethylene glycol, 1 can be used together with ethylene glycol, ammediol, 1, the aliphatic diols, 1 such as 4-butanediol, neopentyl glycol, the alicyclic diols such as 4-cyclohexanedimethanol, the aromatic diols such as the alkylene oxide addition product of bisphenol-A, bisphenol-A, the PAGs such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and glycerine, 1,3-PD, pentaerythrite etc.They can be used alone, or combine two or more use.In addition, diethylene glycol generates owing to being reacted by by-product when the manufacture of ethylene glycol, so usually contain a small amount of diethylene glycol in ethylene glycol.As above-mentioned glycol component, from the view point of heat resistance, preferably except a small amount of by-product diethylene glycol, only form glycol component by ethylene glycol.

Above-mentioned specific PET system resin manufactures basically by by using terephthalic acid (TPA) as the dicarboxylic acid component of main component and the usual manufacture method of the mylar obtained using ethylene glycol as the glycol component of main component.

Namely, have: in esterification groove, carry out esterification as the dicarboxylic acid component of main component with using ethylene glycol as the glycol component of main component by using terephthalic acid (TPA), obtained esterification reaction product is transferred to the direct polymerization method of carrying out polycondensation in polycondensation reaction groove; By using the ester formative derivative of terephthalic acid (TPA) as the dicarboxylic acid component of main component with carry out ester exchange reaction using ethylene glycol as the glycol component of main component in ester exchange reaction groove, obtained product of transesterification reaction is transferred to the ester-interchange method carrying out polycondensation in polycondensation reaction groove.These reactions can be carried out also can carrying out with continous way with batch (-type).In addition, the dicarboxylic acid component beyond terephthalic acid (TPA) can add in the arbitrary moment before esterification or ester exchange reaction terminate, but operation upper preferred with ethylene glycol formed the form of slurry add.

In addition, polycondensation reaction such as uses the phosphorus compounds such as orthophosphoric acid, phosphorous acid and their ester as stabilizing agent, use the polycondensation catalysts such as acylate, alkoxide such as metal oxide or antimony, germanium, zinc, titanium, cobalt, alkaline-earth metal such as such as antimony oxide, germanium dioxide, four germanium oxides, in the temperature of about 240 ~ 290 DEG C, 1 × 10 ²~ 2 × 10 ³carry out under the decompression of about Pa.

The inherent viscosity of above-mentioned specific PET system resin is preferably more than 0.60dl/g and the scope of below 1.20dl/g.By making the inherent viscosity of above-mentioned specific PET system resin in this scope, the multilayer structure making that can obtain intensity He have excellent formability.That is, when the inherent viscosity of PET system resin is less than 0.60dl/g, intensity reduces, and during more than 1.20dl/g, formability reduces.And the inherent viscosity of above-mentioned specific PET system resin is more preferably more than 0.60dl/g and the scope of below 1.00dl/g.

Formed in material containing above-mentioned specific PET system resin as the layer (A) of main component, except above-mentioned specific PET resin, can the suitable additive such as compounding such as pigment dispersing agent, thickener, flow ability modifying agent, surfactant, defoamer, releasing agent, bleeding agent, dyestuff, pigment, fluorescent whitening agent, ultra-violet absorber, antioxidant, anticorrisive agent, mould inhibitor as required.

Then, be described containing the characteristic of above-mentioned specific PET resin as the layer (A) of main component.

< contains layer (B) > of PVA system resin as main component

In mode (z) containing PVA system resin as main component layer (B) with describe in mode (x) before, (y) same, using the specific PVA system resin with the construction unit shown in following general formula (1) as the formation material of main component by use such as melt-shaping is carried out to it and obtains.

[chemical formula 7]

First, the construction unit shown in above-mentioned general formula (1) is described.In 1,2-dihydroxylic alcohols construction unit shown in above-mentioned general formula (1), with in mode (x) before, (y) describe same, the R in formula (1) ¹~ R ³and R ⁴~ R ⁶for hydrogen atom or any monovalent organic radical, they can be mutually the same, also can be different.Wherein, R ¹~ R ³and R ⁴~ R ⁶when being all hydrogen atom, be preferred from the aspect of the copolyreaction of the monomer of fabrication stage and industrial treatability.But, as long as damaging in the scope of resin properties not significantly, R ¹~ R ³and R ⁴~ R ⁶also can be organic group at least partially.As above-mentioned organic group, be not particularly limited, the alkyl of the carbon numbers 1 ~ 4 such as such as preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, also can have the substituting groups such as halogen radical, hydroxyl, ester group, carboxylic acid group, sulfonic group as required further.

In addition, shown in above-mentioned general formula (1) 1, in 2-dihydroxylic alcohols construction unit, from the aspect of excellent heat stability, the aspect not making the crystallinity of PVA excessively reduce, the aspect etc. that do not hinder melt fluidity, the preferred singly-bound of X in formula (1).Wherein, X is that singly-bound refers to that X is certainly as key.

Therefore, in mode (z), in above-mentioned specific PVA system resin, with in mode (x) before, (y) describe same, as 1 shown in above-mentioned general formula (1), 2-dihydroxylic alcohols construction unit, particularly preferably uses the PVA system resin with 1,2-dihydroxylic alcohols construction unit shown in following formula (1a).

[chemical formula 8]

The method for making of the above-mentioned specific PVA system resin adopted in mode (z) and mode (x), (y) is same, such as can by (α) by vinyl acetate and 3, 4-bis-acyloxy-1-butylene special 3, the method of the copolymer saponification of 4-diacetoxy-1-butylene, (β) by vinyl acetate and the copolymer saponification of vinylethylene carbonate and the method for decarbonate, (γ) by vinyl acetate and 2, 2-dialkyl group-4-vinyl-1, the copolymer saponification of 3-dioxolanes and de-ketalization method, (δ) manufacture methods such as the method for the copolymer saponification of vinyl acetate and allylin are manufactured.Wherein, carry out well from polymerization, the characteristic of advantage when easily 1,2-dihydroxylic alcohols construction unit being imported equably the medium manufacture of resin of PVA system and final PVA system resin sets out, preferably adopt above-mentioned manufacture method (α).

The average degree of polymerization of the specific PVA system resin obtained like this (measuring according to JISK6726) is preferably 200 ~ 2000 usually, is particularly preferably 250 ~ 1000, and more preferably 300 ~ 600.That is, this is because, when average degree of polymerization is too low, the tendency that PVA resin becomes fragile is seen; On the contrary, time too high, such as in utilizing the layer of melt-shaping to be formed, mobility is low, sees the tendency of the layer of the thickness be difficult to desired by formation.

In addition, the saponification degree of specific PVA system resin is preferably 80 ~ 100 % by mole usually, is particularly preferably 85 ~ 99.9 % by mole, more preferably 88 ~ 99.9 % by mole.That is, this is because, when saponification degree is too low, see longtime running (maneuverability steady in a long-term such as melt-shaping) and reduce or produce the smelly tendency of acetic acid.Saponification degree in the present invention represents with the rate of change (% by mole) to conversion of hydroxyl such as ester moiety of vinyl esters system monomer.

As above-mentioned base catalyst, such as, can use the base catalyst that the alkali-metal hydroxide such as NaOH, potassium hydroxide, sodium methoxide, caustic alcohol, potassium methoxide, alkoxide are such.As acid catalyst, such as, can use the organic acids such as the inorganic acid aqueous solution such as hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid.The use amount of base catalyst is preferably 1 ~ 100 mM relative to the vinyl acetate construction unit in PVA system resin 1 mole, is particularly preferably 1 ~ 40 mM, more preferably 1 ~ 20 mM.When the use amount of base catalyst is very few, exists and be difficult to tendency saponification degree being increased to target saponification degree, on the contrary, when the use amount of base catalyst is too much, exists and become too high tendency compared with target saponification degree, be difficult to control, thus not preferred.In addition, the temperature such as usual preferably 10 ~ 70 DEG C during saponification is carried out, more preferably 20 ~ 50 DEG C.

And then, as importing 1 in specific PVA system resin, 2-dihydroxylic alcohols bonded amount, i.e. 1 shown in aforementioned formula (1), the content (modification degree) of 2-dihydroxylic alcohols construction unit, such as usually be preferably 0.1 ~ 12 % by mole, be particularly preferably 1 ~ 10 % by mole, more preferably 3 ~ 8 % by mole.That is, when content (modification degree) is very few, fusing point uprises, and sees the tendency that formability may reduce.In addition, when content (modification degree) is too much, the degree of polymerization is difficult to improve during fabrication, sees the tendency that productivity ratio reduces.

Above-mentioned specific PVA system resin can be used alone, and also can combinationally use other PVA system resin in the scope not hindering various characteristic, particularly heat fusing formability.

In addition, in mode (z), as previously mentioned, material is formed as layer (B), preferred use is to have the formation material of specific PVA system resin as main component of the construction unit shown in above-mentioned general formula (1), specifically, above-mentioned specific PVA system resin account for that layer (B) forms material monolithic more than 50 % by weight.

And, from aspects such as the raisings of the raising of adhesiveness between layers, melt-shaping, form material as layer (B), at least one in preferred compounding alkali metal salt and alkali salt.As above-mentioned alkali metal salt, include, for example out the organic acid slaines such as the acetic acid of potassium, sodium etc., propionic acid, butyric acid, laurate, stearic acid, 12-hydroxy stearic acid, oleic acid, behenic acid, the slaine of the inorganic acid such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid of potassium, sodium etc.In addition, as above-mentioned alkali salt, include, for example out the organic acid slaines such as the acetic acid of calcium, magnesium etc., propionic acid, butyric acid, laurate, stearic acid, oleic acid, behenic acid, the slaine of the inorganic acid such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid of calcium, magnesium etc.They can be used alone or combine two or more and use.Wherein, from the aspect of the size of effect corresponding to compounding amount, preferably, as alkali metal salt, be used alone or in combination sodium acetate, as alkali salt, be used alone or in combination magnesium acetate.

And then, layer (B) is formed in material, can suitable compounding other compositions except above-mentioned specific PVA system resin and slaine as required, as other compositions, aliphatic polybasic alcohols and the ethylene oxide adducts thereof such as such as glycerine, ethylene glycol, hexylene glycol can be listed, the plasticizer such as glycitols such as D-sorbite, mannitol, pentaerythrite; The representative examples of saturated aliphatic such as stearmide, ethylene bis stearamide amide compound, the unsaturated aliphatic amide compounds such as oleamide, the aliphatic metal salt such as calcium stearate, dolomol, zinc stearate, molecular weight is the lubriation materials such as low-molecular-weight polyolefin such as low molecular weight polyethylene, low-molecular-weight polypropylene of about 500 ~ 10000; And the inorganic acid such as boric acid, phosphoric acid; Antioxidant; Heat stabilizer; Light stabilizer; Ultra-violet absorber; Colouring agent; Antistatic additive; Surfactant; Anticorrisive agent; Antiseptic; Antiblocking agent; Slip agent; Filler etc.

Above-mentioned layer (B) forms that material is such as described below to be obtained.That is, compounding various composition and obtaining as required wherein after modulation above-mentioned specific PVA system resin.

" about multilayer structure making "

Then, form to the above-mentioned layer (A) in occupation mode (x) ~ (z) multilayer structure making of the present invention that material and layer (B) form material and formed to be described.

Adjoin with this layer (A) containing the layer (A) of specific PET system resin as main component as long as multilayer structure making of the present invention possesses, and containing the structure that the PVA system resin with specific construction unit is laminated as the layer (B) of main component, such as, when being considered as the purposes of various formed products formation material, the 3-tier architecture of preferably layer (A)/layer (B)/layer (A), and layer (A)/layer (B)/layer (A)/layer (B)/layer (A), the layer that layer (A) and layer (B) stack gradually forms by layer (A)/layer (B)/layer (A)/layer (B)/layer (A)/layer (B)/layers (A) etc.Wherein, for when needing the purposes of barrier etc., the two ends surface part of multilayer structure making is preferably formed layer (A).

The Thickness Ratio [layer (A)/layer (B)] of above-mentioned layer (A) and layer (B) is preferably 30/70 ~ 95/5 usually, is particularly preferably 40/60 ~ 90/10, and more preferably 50/50 ~ 80/20.That is, compared with layer (B), when layer (A) is crossed thin, the tendency of the intensity deficiency of obtained multilayer structure making is seen.

And then, as the stepped construction of multilayer structure making of the present invention, be not only laminated with layer (A) and layer (B), also can according to other layers beyond the layer laminate such as object, purposes (A) and layer (B).As other layers above-mentioned, include, for example out by various thermoplastic resin formed weave cotton cloth, layer that net, woven wire, paper etc. are formed.

" autofrettage of multilayer structure making "

Then, the manufacture method of multilayer structure making of the present invention is described.

As the manufacture method of multilayer structure making of the present invention, each moulding material of preparation layer (A) and layer (B) can be listed, carry out the method for coextrusion or the method for injection altogether by melt-shaping.Particularly as the autofrettage of plural layers, multi-layer sheet, coetrusion is more suitable, specifically, the known methods such as the outer bonding method (die external adhesion process) of multiple flow passages modulus method (multi-manifold die process), feed block method (feed block process), multiple-grooved modulus method (multi-slot die process), mould can be adopted.As the shape of the mould in above-mentioned coetrusion, T mould, circle mould etc. can be used.

In addition, as the autofrettage of bottle, cup, pallet etc., preferably adopt injection altogether, particularly as the autofrettage of bottle, from the view point of productivity ratio, preferably inject twin-screw draw blow molding method altogether.

Below, common injection twin-screw draw blow molding method is described in detail.

In the above-mentioned twin-screw of injection altogether draw blow molding method, first, to the 3-tier architecture of at least layer (A)/layer (B)/layer (A), namely using containing specific PVA system resin as the layer (B) of main component as intermediate layer and the parison (also referred to as container precursor or preform) of the 3-tier architecture body arranging the layer (A) using specific PET system resin as main component in its both sides and formed carry out common injection moulding to make.Then, while heat this parison and remain uniform temperature edge longitudinally carry out mechanical stretching in blow mold, simultaneously or be successively blown into forced air and make it along the circumferential direction expand.

First, about the making of parison with above-mentioned sandwich construction, usually, use the injection machine with 2 injection cylinder and multi-layer flow channels system, from each injection cylinder, by multi-layer flow channels system simultaneously or the staggering time layer (A) of injecting melting in single mold forms material and layer (B) forms material, the parison of this sandwich construction is obtained thus.

Such as, first the layer (A) that injection two is outer forms material, then inject the layer (B) becoming intermediate layer and form material, injection ormal weight layer (B) form material after, continue injecting layer (A) again and form material, obtain thus being made up of the 3-tier architecture of layer (A)/layer (B)/layer (A) and be sealed with middle layer (B) in the layer of both sides (A) have die bed base.

As the injection moulding condition of above-mentioned parison, the injection moulding temperature that layer (B) forms material is preferably 150 ~ 300 DEG C usually, more preferably 160 ~ 270 DEG C, is particularly preferably 170 ~ 230 DEG C.Namely, when above-mentioned injection moulding temperature is too low, sometimes the melting that layer (B) forms material becomes insufficient, contrary too high time, see the thermal decomposition forming material because of layer (B) and cause the aesthetic appearance of obtained twin-screw stretch blow bottle to worsen or foul smell becomes significant tendency.

On the other hand, the injection moulding temperature that layer (A) forms material is preferably 230 ~ 350 DEG C usually, more preferably 250 ~ 330 DEG C, is particularly preferably 270 ~ 310 DEG C.Namely, when above-mentioned injection moulding temperature is too low, sometimes the melting that layer (A) forms material becomes insufficient, contrary too high time, see the thermal decomposition forming material because of layer (A) and cause the aesthetic appearance of obtained twin-screw stretch blow bottle to worsen or foul smell becomes significant tendency.

And then layer (A) forms material and layer (B) forms material and the temperature in the multi-layer flow channels portion of stream is preferably 230 ~ 350 DEG C usually, more preferably 250 ~ 330 DEG C, is particularly preferably 270 ~ 310 DEG C.Namely, when said temperature is too low, sometimes the melting that layer (A) forms material becomes insufficient, contrary too high time, see and cause the aesthetic appearance of obtained twin-screw stretch blow bottle to worsen or foul smell becomes significant tendency because layer (A) forms thermal decomposition that material and layer (B) form material.

In addition, layer (A) forms the temperature that material and layer (B) form the mould that material flows into and is usually preferably 0 ~ 80 DEG C, more preferably 5 ~ 60 DEG C, is particularly preferably 10 ~ 30 DEG C.Namely, when said temperature is too low, mould condenses sometimes, the tendency that the aesthetic appearance seeing obtained parison or twin-screw stretch blow bottle reduces, contrary too high time, see the tendency that the blow molding of obtained parison reduces or the transparency of twin-screw stretch blow bottle obtained reduces.

Like this, obtain the parison with sandwich construction, then, directly longitudinally carried out by above-mentioned parison mechanical stretching or limit to heat again and in blow mold, remain uniform temperature edge longitudinally carry out mechanical stretching, simultaneously or be successively blown into forced air and make it along the circumferential direction expand, target twin-screw stretch blow bottle is obtained thus.

And, can list parison that injection moulding is obtained immediately with this tepid state send into again carry out blow molding in heating process mode (pattern of fever base method), the parison of injection moulding is sent into the mode (cold parison process) of carrying out blow molding in heating process after keeping certain hour under room temperature state again, all can adopt according to both objects, usually, from the aspect of productivity ratio excellence, preferably adopt above-mentioned cold parison process.

As the method heated again above-mentioned parison, include, for example out the method that the heaters such as use infrared heater or engine block heater carry out heating.The temperature of the parison of heating is preferably 80 ~ 140 DEG C usually, more preferably 85 ~ 130 DEG C, is particularly preferably 90 ~ 120 DEG C.That is, when said temperature is too low, the uniformity of stretching becomes insufficient, see the shape of obtained laminated vessel, thickness becomes uneven tendency, on the contrary, when temperature is too high, layer (A) forms the crystallization aggravation of material, sees the tendency of obtained laminated vessel generation albefaction.

Then, use the parison after heating again, carry out twin-screw stretching, obtain target twin-screw stretch blow bottle thus.Usually, utilize piston or pull bar etc. longitudinally after mechanical stretching about 1 ~ 7 times, utilize compressed-air power transversely to stretch about 1 ~ 7 times, obtain target twin-screw stretch blow bottle thus.Above-mentioned longitudinal stretching and horizontal stretching can be carried out simultaneously, also can successively carry out.In addition, also compressed-air power can be combinationally used when the stretching of longitudinal direction.

" purposes of the present invention "

Multilayer structure making of the present invention is suitable for various packaging material, the various shape of containers such as packaging material for food, pharmaceuticals packaging material, industrial drug packing material, pesticides packaging material and becomes in the purposes of material.Be suitable for especially and effectively utilize the shape of container of its characteristic to become material.And then, in multilayer structure making of the present invention, due to the water-soluble excellence of PVA system resin used in the layer (B), so by above-mentioned multilayer structure making is cut, washes, can easily only recycled PET system resin, recirculation property excellence.

Embodiment

Below, the present invention will be described to list embodiment, and the present invention is not limited to the record of embodiment, can change in the scope not exceeding its purport.In addition, there is " part " in example, " % " all refer to weight basis unless otherwise specified.

" embodiment in mode (x) "

The modulation > of < material

< layer (A) forms material >

The manufacture method of above-mentioned specific PET system resin and the assay method of each physical property and evaluating carries out by the following method.

(1) inherent viscosity (IV)

Be that PET system resin samples is about 0.25g and is dissolved into phenol/1 by the mode of 1.00g/dL according to concentration, 1,2, the mixed liquor of 2-tetrachloroethanes (weight ratio 1/1) is about in 25mL, then be cooled to 30 DEG C and kept, utilize full-automatic solution viscosity meter (central physics and chemistry Inc. " 2CH type DT 504 "), measure sample solution fall number of seconds and only solvent fall number of seconds, calculated by following formula (2).

IV＝((1+4KH·ηsp) ^0.5-1)/(2KH·C)…(2)

Wherein, η sp=η/η 0-1, η be sample solution fall number of seconds, what η 0 was only solvent falls number of seconds, and C is sample solution concentration (g/dL), and KH is Huggins constant.KH adopts 0.33.In addition, the dissolution conditions of sample is at 110 DEG C 30 minutes.

(2) end carboxy concentration (AV)

After PET system resin samples is pulverized, utilize air drier at 140 DEG C dry 15 minutes, room temperature is cooled in drier, from gained sample accurate weighing 0.1g to test tube, add phenmethylol 3mL, dissolve 3 minutes at 195 DEG C while be blown into drying nitrogen limit, then, add chloroform 5mL lentamente, be cooled to room temperature.In this solution, add 1 ~ 2 phenolic red indicator, while be blown into drying nitrogen limit under agitation carry out titration by the benzyl alcohol solution of the NaOH of 0.1 equivalent, become the moment of redness by yellow as terminal.In addition, as blank, do not use PET system resin samples and implement same operation, being calculated by following formula.

AV (equivalent/ton)=(A-B) × 0.1 × f/W

(wherein, the amount (μ L) of the benzyl alcohol solution of the NaOH of 0.1 equivalent of A needed for titration, the amount (μ L) of the benzyl alcohol solution of the NaOH of 0.1 equivalent of B needed for blank titration, W is the amount (g) of PET system resin samples, and f is the titer of the benzyl alcohol solution of the NaOH of 0.1 equivalent.〕

In addition, about the titer (f) of the benzyl alcohol solution of the NaOH of 0.1 equivalent, methyl alcohol 5mL is gathered in test tube, add 1 ~ 2 phenol red ethanolic solution as indicator, color transition point is titrated to the benzyl alcohol solution 0.4mL of the NaOH of 0.1 equivalent, then, gather and the aqueous hydrochloric acid solution adding 0.1 known equivalent of 0.2mL titer as titer, be again titrated to color transition point by the benzyl alcohol solution of the NaOH of 0.1 equivalent.(above operation limit is blown into drying nitrogen limit and carries out.)

Titer (f) is calculated by following formula.

The titer (μ L) of the benzyl alcohol solution of the NaOH of collection capacity (μ L)/0.1 equivalent of the aqueous hydrochloric acid solution of titer × 0.1 equivalent of the aqueous hydrochloric acid solution of titer (f)=0.1 equivalent

(1) manufacture of PET system resin (IS654)

As described below manufacture to be made up of terephthalic acid (TPA) and M-phthalic acid and the PET system resin that formed with the glycol component be made up of ethylene glycol of the dicarboxylic acid component of 30.0 % by mole that the copolymerization ratios of M-phthalic acid is dicarboxylic acid component's entirety.

By dimethyl terephthalate (DMT) (below sometimes referred to as " DMT ") 34.9kg, DMIP (below sometimes referred to as " DMI ") 14.9kg and ethylene glycol (below sometimes referred to as " EG ") 35.4kg joins to be possessed mixer and distillates in the stainless steel autoclave of pipe, wherein, ethylene glycol is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the calcium acetate of 300 weight ppm again, at 250 DEG C, to remove the methyl alcohol of by-product under the condition of absolute manometer 101kPa, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the antimony trioxide catalyst of 240 weight ppm and the triethyl phosphate of 350 weight ppm, 280 DEG C, carry out 8 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, water-cooled limit, limit carries out cutting and making particle, obtains PET system resin (IS654) of AV value 33 equivalents/ton, inherent viscosity 0.72.

(2) manufacture of PET system resin (IG395Z)

As described below manufacture to be made up of terephthalic acid (TPA) and M-phthalic acid and the PET system resin that formed with the glycol component be made up of ethylene glycol of the dicarboxylic acid component of 15.0 % by mole that the copolymerization ratios of M-phthalic acid is dicarboxylic acid component's entirety.

DMT:42.3kg, DMI:7.5kg and EG:35.4kg are joined and possesses mixer and distillate in the stainless steel autoclave of pipe, wherein, EG is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the calcium acetate of 300 weight ppm again, 250 DEG C, with the condition of absolute manometer 101kPa under remove the methyl alcohol of by-product, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the germanium dioxide catalyst of 150 weight ppm and the triethyl phosphate of 240 weight ppm, 280 DEG C, carry out 6 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, carry out cutting and making particle while carry out water-cooled limit.By obtained copolymer polyester resin particle under nitrogen atmosphere, at 100 DEG C after Pre-crystallizing 8 hours, in inertia stove (TABAI ESPEC Inc. INERT OVEN IPHH201), carry out 10 hours solid phase polycondensations at 195 DEG C under nitrogen circulation, obtain PET system resin (IG395Z) of AV value 28 equivalents/ton, inherent viscosity 0.70.

(3) manufacture of PET system resin (IG229Z)

As described below manufacture to be made up of terephthalic acid (TPA) and M-phthalic acid and the PET system resin that formed with the glycol component be made up of ethylene glycol of the dicarboxylic acid component of 12.0 % by mole that the copolymerization ratios of M-phthalic acid is dicarboxylic acid component's entirety.

DMT:43.8kg, DMI:6.0kg and EG:35.4kg are joined and possesses mixer and distillate in the stainless steel autoclave of pipe, wherein, EG is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the calcium acetate of 300 weight ppm again, 250 DEG C, with the condition of absolute manometer 101kPa under remove the methyl alcohol of by-product, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the germanium dioxide catalyst of 150 weight ppm and the triethyl phosphate of 240 weight ppm, 280 DEG C, carry out 8 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, carry out cutting and making particle while carry out water-cooled limit.By obtained copolymer polyester resin particle under nitrogen atmosphere, at 100 DEG C after Pre-crystallizing 8 hours, in inertia stove (TABAI ESPEC Inc. INERT OVEN IPHH201), carry out 24 hours solid phase polycondensations at 195 DEG C under nitrogen circulation, obtain PET system resin (IG229Z) of AV value 12 equivalents/ton, inherent viscosity 0.96.

(4) manufacture of PET system resin (GG500)

The PET system resin manufacturing dicarboxylic acid component and the glycol component be made up of ethylene glycol be only made up of terephthalic acid (TPA) as described below.

DMT:49.8kg and EG:33.1kg is joined and possesses mixer and distillate in the stainless steel autoclave of pipe, wherein, EG is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the calcium acetate of 300 weight ppm again, 250 DEG C, with the condition of absolute manometer 101kPa under remove the methyl alcohol of by-product, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the germanium dioxide catalyst of 150 weight ppm and the triethyl phosphate of 240 weight ppm, 280 DEG C, carry out 6 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, carry out cutting and making particle while carry out water-cooled limit.By obtained copolymer polyester resin particle under nitrogen atmosphere, at 100 DEG C after Pre-crystallizing 8 hours, in inertia stove (TABAI ESPEC Inc. INERT OVEN IPHH201), carry out 10 hours solid phase polycondensations at 215 DEG C under nitrogen circulation, obtain PET system resin (GG500) of AV value 10 equivalents/ton, inherent viscosity 0.77.

< layer (B) forms material >

(1) manufacture of PVA system resin (B1-x)

To in the retort possessing reflux condenser, dropping funel, mixer, add vinyl acetate 305.0g, methyl alcohol 219.8g, 3,4-diacetoxy-1-butylene 19.2g, make temperature increase while stirring under nitrogen flowing, the 4% methanol solution 37.8g adding new peroxide tert-butyl caprate (102 minutes half-life) with 610 minutes is polymerized.In addition, when from polymerization through 30 minutes when, added vinyl acetate 480g, 3,4-diacetoxy-1-butylene 28.8g with 420 minutes, then carry out being polymerized for 105 minutes.When the aggregate rate of vinyl acetate reaches 89.5%, adding the p methoxy phenol 38ppm (vinyl acetate relative to adding) as polymerization inhibitor, terminating polymerization.Then, by the method being blown into methanol vapor, unreacted vinyl acetate monomer is removed to outside system, obtains the methanol solution of copolymer.

Then, the concentration of copolymer is adjusted to 66% by the dilution of this solution with methanol, join in kneader, while solution temperature is remained on 40 DEG C, while carry out saponification with 2% methanol solution of the ratio relative to the total amount 1 mole of the vinyl acetate in copolymer and 3,4-diacetoxy-1-butylene being 12 mMs interpolation NaOH.While carrying out saponification saponified with graininess separate out and after becoming slurry, interpolation is the acetic acid of 1 equivalent relative to added amount of sodium hydroxide, adding methyl alcohol again makes the resin concentration in slurry reach 9%, stir 15 minutes in kneader, filter, dry in air drier, in methyl alcohol, dispersion is filtered after stirring again, obtains PVA system resin (B1-x).

The saponification degree of PVA system resin (B1-x) obtained is with residual vinyl acetate and residual 3, the quantity of alkali consumption needed for hydrolysis of 4-diacetoxy-1-butylene is analyzed, result is 98.8 % by mole, and average degree of polymerization is analyzed according to JISK6726, and result is 450.In addition, the import volume of the side chain containing 1,2-dihydroxylic alcohols structure passes through ¹h-NMR spectrum (solvent: DMSO-d ₆, interior standard: tetramethylsilane) carry out measuring and calculating, result is 3 % by mole.In addition, namely the accessory substance of saponification is not 0.02 % by mole by the content of the sodium acetate utilizing the washing of methyl alcohol to remove.

(2) manufacture of PVA system resin (B2-x)

According to the compounding magnesium acetate of the amount (Mg (Ac) relative to its entire infrastructure unit being 0.039 % by mole in PVA system resin (B1-x) ₂), use double screw extruder (TECHNOVEL CORPORATION KZW-15-60MG, screw diameter 15mm, L/D=60), at resin temperature 210 DEG C, melting mixing is carried out to it, obtain granular PVA system resin (B2-x).

(3) manufacture of PVA system resin (B3-x)

According to the compounding magnesium acetate of the amount (Mg (Ac) being respectively 0.039 % by mole, 0.17 % by mole relative to its entire infrastructure unit in PVA system resin (B1-x) ₂), sodium acetate (NaAc), use double screw extruder (TECHNOVEL CORPORATION KZW-15-60MG, screw diameter 15mm, L/D=60), at resin temperature 210 DEG C, melting mixing is carried out to it, obtain granular PVA system resin (B3-x).

(embodiment 1)

The 3-tier architecture body > that < is made up of layer (A) and layer (B)

Material is formed as the layer (A) shown in following, use above-mentioned PET system resin (IS654), material is formed as layer (B), use above-mentioned PVA system resin (B1-x), utilize there is the T mould of 2 kinds 3 layers melt extrude forming machine, made the duplexer (film-form) (gross thickness 100 μm) of the 3-tier architecture be made up of layer (A)/layer (B)/layer (A) of the thickness 40 μm of thickness 20 μm, layer (A) of thickness 40 μm, layer (B) of layer (A).

In addition, at the resin temperature 240 DEG C of the resin temperature 260 ~ 280 DEG C of PET system resin, PVA system resin, extrude with mould temperature 260 DEG C, the roller cooling of the multi-layer resinous use 40 DEG C of film-form will be extruded into, obtain multilayer structure making.

< peel resistance (T stripping) >

Use the 3-tier architecture body (film) obtained, measure the peel strength of layer (A) and layer (B) under the following conditions.The results are shown in table 1 described later.

Sample: 15mm is wide, 200mm is long

Device: Shimadzu Corporation Autograph AG-100

Assay method: T stripping method (n=5)

Peeling rate: 100mm/min

(embodiment 2)

Form material and PET system resin as layer (A), the copolymerization ratios of use M-phthalic acid is the above-mentioned IG395Z (AV value 28) of 15.0 % by mole.In addition, manufacture 3-tier architecture body similarly to Example 1, similarly evaluate.The results are shown in table 1 described later.

(comparative example 1)

Form material and PET system resin as layer (A), the copolymerization ratios of use M-phthalic acid is the above-mentioned IG229Z (AV value 12) of 12.0 % by mole.In addition, manufacture 3-tier architecture body similarly to Example 1, similarly evaluate.The results are shown in table 1 described later.

(comparative example 2)

Material and PET system resin is formed, the above-mentioned GG 500 (AV value 10) of (copolymerization ratios of M-phthalic acid is 0 % by mole) that use dicarboxylic acid component to be only made up of terephthalic acid (TPA) as layer (A).In addition, manufacture 3-tier architecture body similarly to Example 1, similarly evaluate.The results are shown in following table 1.

Table 1

< mode [x] >

※ represents the copolymerization ratios (addition during polymerization) of the dicarboxylic acids beyond the terephthalic acid (TPA) in dicarboxylic acid component.

From the above results, the adhesiveness between layers of all embodiments is all excellent.

On the other hand, comparative example 1,2 and embodiment 1,2 corresponding, copolymerization ratios due to M-phthalic acid is low to moderate 12.0 % by mole or be only made up of terephthalic acid (TPA) as dicarboxylic acid component, so do not produce because the crystalline crystallinity caused in a jumble reduces, the contraction of layer (A) is large, so as a result, the value of T stripping is low, peel resistance is poor.

(embodiment 3)

As the PVA system resin being used as layer (B) in embodiment 1 and being formed material, use PVA system resin (B2-x), manufacture 3-tier architecture body similarly to Example 1 in addition, similarly evaluate.The results are shown in table 2 described later.

(embodiment 4)

As the PVA system resin being used as layer (B) in embodiment 3 and being formed material, use PVA system resin (B3-x), obtain PVA system resin (B3) in addition similarly to Example 3, similarly manufacture 3-tier architecture body, similarly evaluate.The results are shown in following table 2.

Table 2

< mode [x] >

From the above results, by compounding alkali metal salt further in PVA system resin and alkali salt, thus the more excellent multilayer structure making of adhesiveness between layers is obtained.

" embodiment in mode (y) "

The modulation > of < material

< layer (A) forms material >

(1) inherent viscosity (IV)

Be that PET system resin samples is about 0.25g and is dissolved into phenol/1 by the mode of 1.00g/dL according to concentration, 1,2, the mixed liquor of 2-tetrachloroethanes (weight ratio 1/1) is about in 25mL, then be cooled to 30 DEG C and kept, utilize full-automatic solution viscosity meter (central physics and chemistry Inc. " 2CH type DT504 "), measure sample solution fall number of seconds and only solvent fall number of seconds, calculated by following formula (2).

IV＝((1+4KH·ηsp) ^0.5-1)/(2KH·C)…(2)

(2) end carboxy concentration (AV)

After PET system resin samples is pulverized, utilize air drier at 140 DEG C dry 15 minutes, room temperature is cooled in drier, from gained sample accurate weighing 0.1g to test tube, add phenmethylol 3mL, dissolve 3 minutes at 195 DEG C while be blown into drying nitrogen limit, then, add chloroform 5mL lentamente, be cooled to room temperature.In this solution, add 1 ~ 2 phenolic red indicator, under agitation utilize the benzyl alcohol solution of the NaOH of 0.1 equivalent to carry out titration while be blown into drying nitrogen limit, become the moment of redness from yellow as terminal.In addition, as blank, do not use PET system resin samples and implement same operation, being calculated by following formula.

AV (equivalent/ton)=(A-B) × 0.1 × f/W

Titer (f) is calculated by following formula.

(1) manufacture of PET system resin (IG226S)

As described below manufacture to be made up of terephthalic acid (TPA) and M-phthalic acid and the PET resin that formed with the glycol component be made up of ethylene glycol of the dicarboxylic acid component of 12.0 % by mole that the copolymerization ratios of M-phthalic acid is dicarboxylic acid component's entirety.

By dimethyl terephthalate (DMT) (below sometimes referred to as " DMT ") 43.8kg, DMIP (below sometimes referred to as " DMI ") 6.0kg and ethylene glycol (below sometimes referred to as " EG ") 35.4kg joins to be possessed mixer and distillates in the stainless steel autoclave of pipe, wherein, ethylene glycol is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the calcium acetate of 300 weight ppm again, at 250 DEG C, to remove the methyl alcohol of by-product under the condition of absolute manometer 101kPa, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the germanium dioxide catalyst of 150 weight ppm and the triethyl phosphate of 240 weight ppm, 280 DEG C, carry out 8 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, carry out cutting and making particle while carry out water-cooled limit.By obtained copolymer polyester resin particle under nitrogen atmosphere, at 100 DEG C after Pre-crystallizing 8 hours, in inertia stove (TABAI ESPEC Inc. INERT OVEN IPHH201), carry out 12 hours solid phase polycondensations at 195 DEG C under nitrogen circulation, obtain PET system resin (IG226S) of AV value 24 equivalents/ton, inherent viscosity 0.82.

(2) manufacture of PET resin (BK-6180C)

As described below manufacture to be made up of terephthalic acid (TPA) and M-phthalic acid and the PET resin that formed with the glycol component be made up of ethylene glycol of the dicarboxylic acid component of 2.0 % by mole that the copolymerization ratios of M-phthalic acid is dicarboxylic acid component's entirety.

DMT:48.8kg, DMI:1.0kg and EG:33.1kg are joined and possesses mixer and distillate in the stainless steel autoclave of pipe, wherein, EG is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the calcium acetate of 300 weight ppm again, 250 DEG C, with the condition of absolute manometer 101kPa under remove the methyl alcohol of by-product, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the germanium dioxide catalyst of 150 weight ppm and the triethyl phosphate of 240 weight ppm, 280 DEG C, carry out 8 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, carry out cutting and making particle while carry out water-cooled limit.By obtained copolymer polyester resin particle under nitrogen atmosphere, at 100 DEG C after Pre-crystallizing 8 hours, in inertia stove (TABAI ESPEC Inc. INERT OVEN IPHH201), carry out 20 hours solid phase polycondensations at 215 DEG C under nitrogen circulation, obtain PET system resin (BK6180C) of AV value 8 equivalents/ton, inherent viscosity 0.83.

(3) manufacture of PET resin (GG500)

In the same manner as the PET resin (GG500) used in the embodiment in mode (x) before, the PET resin manufacturing the dicarboxylic acid component that is only made up of terephthalic acid (TPA) and formed with the glycol component be made up of ethylene glycol as described below.

< layer (B) forms material >

(1) manufacture of PVA system resin (B1-y)

To in the retort possessing reflux condenser, dropping funel, mixer, add vinyl acetate 321.4g, methyl alcohol 241.1g, 3,4-diacetoxy-1-butylene 38.6g, make temperature increase while stirring under nitrogen flowing, the 4% methanol solution 37.8g adding new peroxide tert-butyl caprate (102 minutes half-life) with 610 minutes is polymerized.In addition, when from polymerization through 35 minutes when, added vinyl acetate 571.4g, 3,4-diacetoxy-1-butylene 68.6g with 480 minutes, then carry out being polymerized for 105 minutes.When the aggregate rate of vinyl acetate reaches 89.5%, adding the p methoxy phenol 38ppm (vinyl acetate relative to adding) as polymerization inhibitor, terminating polymerization.Then, by the method being blown into methanol vapor, unreacted vinyl acetate monomer is removed to outside system, obtains the methanol solution of copolymer.

Then, the concentration of copolymer is adjusted to 66% by the dilution of this solution with methanol, join in kneader, while solution temperature is remained on 40 DEG C, while carry out saponification with 2% methanol solution of the ratio relative to the total amount 1 mole of the vinyl acetate in copolymer and 3,4-diacetoxy-1-butylene being 12 mMs interpolation NaOH.While carrying out saponification saponified with graininess separate out and after becoming slurry, interpolation is the acetic acid of 1 equivalent relative to added amount of sodium hydroxide, adding methyl alcohol again makes the resin concentration in slurry reach 9%, stir 15 minutes in kneader, filter, in methyl alcohol, dispersion is filtered after stirring again, dry in air drier, obtains PVA system resin.

The saponification degree of the PVA system resin obtained is analyzed with the quantity of alkali consumption needed for the hydrolysis of residual vinyl acetate and residual 3,4-diacetoxy-1-butylene, and result is 98.7 % by mole, and average degree of polymerization is analyzed according to JISK6726, and result is 450.In addition, the import volume of the side chain containing 1,2-dihydroxylic alcohols structure passes through ¹h-NMR spectrum (solvent: DMSO-d ₆, interior standard: tetramethylsilane) carry out measuring and calculating, result is 6 % by mole.In addition, namely the accessory substance of saponification is not 0.02 % by mole by the content of the sodium acetate utilizing the washing of methyl alcohol not remove.

According to the compounding magnesium acetate of the amount (Mg (Ac) being respectively 0.039 % by mole, 0.17 % by mole relative to its entire infrastructure unit in obtained PVA system resin ₂), sodium acetate (NaAc), use double screw extruder (TECHNOVEL CORPORATION KZW-15-60MG, screw diameter 15mm, L/D=60), at resin temperature 210 DEG C, melting mixing is carried out to it, obtain granular PVA system resin (B1-y).

(2) manufacture of PVA system resin (B2-y ~ B8-y)

In the manufacture of PVA system resin (B1-y), the compounding amount of magnesium acetate and sodium acetate is set as shown in table 3 described later, similarly obtains granular PVA system resin (B2-y ~ B8-y) in addition.

In addition, about B8-y, dolomol is used to replace magnesium acetate.

(3) manufacture of PVA system resin (B9-y)

Then, the concentration of copolymer is adjusted to 66% by the dilution of this solution with methanol, join in kneader, while solution temperature is remained on 40 DEG C, while carry out saponification with 2% methanol solution of the ratio relative to the total amount 1 mole of the vinyl acetate in copolymer and 3,4-diacetoxy-1-butylene being 12 mMs interpolation NaOH.While carrying out saponification saponified with graininess separate out and after becoming slurry, interpolation is the acetic acid of 1 equivalent relative to added amount of sodium hydroxide, adding methyl alcohol again makes the resin concentration in slurry reach 9%, stir 15 minutes in kneader, filter, dry in air drier, obtain PVA system resin.

The saponification degree of the PVA system resin obtained is analyzed with the quantity of alkali consumption needed for the hydrolysis of residual vinyl acetate and residual 3,4-diacetoxy-1-butylene, and result is 98.8 % by mole, and average degree of polymerization is analyzed according to JISK6726, and result is 450.In addition, the import volume of the side chain containing 1,2-dihydroxylic alcohols structure passes through ¹h-NMR spectrum (solvent: DMSO-d ₆, interior standard: tetramethylsilane) carry out measuring and calculating, result is 3 % by mole.In addition, the content of sodium acetate is 0.02 % by mole.

According to the compounding magnesium acetate of the amount (Mg (Ac) relative to its entire infrastructure unit being 0.039 % by mole in obtained PVA system resin ₂), use double screw extruder (TECHNOVEL CORPORATION KZW-15-60MG, screw diameter 15mm, L/D=60), at resin temperature 210 DEG C, melting mixing is carried out to it, obtain granular PVA system resin (B9-y).

(4) manufacture of PVA system resin (B10-y)

In the manufacture of PVA system resin (B9-y), the compounding amount of magnesium acetate and sodium acetate is set as shown in table 3, similarly obtains granular PVA system resin (B10-y) in addition.

(embodiment 5)

The 3-tier architecture body > that < is made up of layer (A) and layer (B)

Material is formed as the layer (A) shown in following, use above-mentioned PET system resin (IS226S), material is formed as layer (B), use above-mentioned PVA system resin (B1-y), utilize there is the T mould of 2 kinds 3 layers melt extrude forming machine, made the duplexer (film-form) (gross thickness 100 μm) of the 3-tier architecture be made up of layer (A)/layer (B)/layer (A) of the thickness 40 μm of thickness 20 μm, layer (A) of thickness 40 μm, layer (B) of layer (A).

< peel resistance (T stripping) >

In the same manner as the embodiment in mode (x) before, use the 3-tier architecture body (film) obtained, measure the peel strength of layer (A) and layer (B) under the following conditions.Show the result in following table 3.

Sample: 15mm is wide, 200mm is long

Device: Shimadzu Corporation Autograph AG-100

Assay method: T stripping method (n=5)

Peeling rate: 100mm/min

(embodiment 6 ~ 13, comparative example 3 ~ 5)

Form material and PET system resin and layer (B) as the layer (A) in embodiment 5 and form material and PVA system resin, use the resin shown in following table 3, manufacture 3-tier architecture body similarly to Example 5 in addition, similarly evaluate.Show the result in following table 3.

Table 3

< mode [y] >

※ 1 represents the copolymerization ratios (addition during polymerization) of the dicarboxylic acids beyond the terephthalic acid (TPA) in dicarboxylic acid component.

※ 2 represents that use dolomol is as alkali salt.

On the other hand, comparative example 3 due to the compounding amount of slaine few to 0.02 % by mole, so do not obtain the effect as catalyst action, as a result, adhesiveness between layers is poor.In addition, comparative example 4 due to the compounding amount of slaine too much, be 1.2 % by mole, so the gas that the thermal decomposition thinking because of PVA system resin causes produces in a large number, comprise a lot of bubble in layer, the multilayer structure making that can evaluate cannot be obtained.

In addition, comparative example 5 is only made up of terephthalic acid (TPA) due to PET resin layer (A), so as a result, the value peeled off of T is low, peel resistance is poor.

" embodiment in mode (z) "

The modulation > of < material

< layer (A) forms material >

The manufacture method of above-mentioned specific PET system resin and the assay method of each physical property and evaluate by the following method.

(1) inherent viscosity (IV)

Be that PET system resin samples is about 0.25g and is dissolved into phenol/1 by the mode of 1.00g/dL according to concentration, 1,2, the mixed liquor of 2-tetrachloroethanes (weight ratio 1/1) is about in 25mL and is then cooled to 30 DEG C and is kept, utilize full-automatic solution viscosity meter (central physics and chemistry Inc. " 2CH type DT504 "), measure sample solution fall number of seconds and only solvent fall number of seconds, calculated by following formula (2).

IV＝((1+4KH·ηsp) ^0.5-1)/(2KH·C)…(2)

(2) end carboxy concentration (AV)

AV (equivalent/ton)=(A-B) × 0.1 × f/W

Titer (f) is calculated by following formula.

(1) manufacture of PET system resin (MMA15)

As described below manufacture to be made up of terephthalic acid (TPA) and M-phthalic acid and the PET resin that formed with the glycol component be made up of ethylene glycol of the dicarboxylic acid component of 20 % by mole that the copolymerization ratios of M-phthalic acid is dicarboxylic acid component's entirety.

By dimethyl terephthalate (DMT) (below sometimes referred to as " DMT ") 39.8kg, DMIP (below sometimes referred to as " DMI ") 10.0kg and ethylene glycol (below sometimes referred to as " EG ") 35.4kg joins to be possessed mixer and distillates in the stainless steel autoclave of pipe, wherein, ethylene glycol is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the magnesium acetate of 700 weight ppm again, at 250 DEG C, to remove the methyl alcohol of by-product under the condition of absolute manometer 101kPa, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the tetrabutyl titanate ester catalyst of 150 weight ppm and the triethyl phosphate of 320 weight ppm, 280 DEG C, carry out 8 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, water-cooled limit, limit carries out cutting and making particle, obtains PET system resin (MMA15) of AV value 35 equivalents/ton, inherent viscosity 0.70.

(2) manufacture of PET system resin (GG500)

In the same manner as the PET resin (GG500) used in the embodiment in mode (x) before, (y), the PET resin manufacturing the dicarboxylic acid component that is only made up of terephthalic acid (TPA) and formed with the glycol component be made up of ethylene glycol as described below.

DMT49.8kg and EG33.1kg is joined and possesses mixer and distillate in the stainless steel autoclave of pipe, wherein, EG is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the calcium acetate of 300 weight ppm again, 250 DEG C, with the condition of absolute manometer 101kPa under remove the methyl alcohol of by-product, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the germanium dioxide catalyst of 150 weight ppm and the triethyl phosphate of 240 weight ppm, 280 DEG C, carry out 6 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, carry out cutting and making particle while carry out water-cooled limit.By obtained copolymer polyester resin particle under nitrogen atmosphere, at 100 DEG C after Pre-crystallizing 8 hours, in inertia stove (TABAI ESPEC Inc. INERT OVEN IPHH201), carry out 10 hours solid phase polycondensations at 215 DEG C under nitrogen circulation, obtain PET system resin (GG500) of AV value 10 equivalents/ton, inherent viscosity 0.77.

(3) manufacture of PET resin (GF101X)

The PET resin manufacturing the dicarboxylic acid component that is only made up of terephthalic acid (TPA) and formed with the glycol component be made up of ethylene glycol as described below.

DMT49.8kg and EG33.1kg is joined and possesses mixer and distillate in the stainless steel autoclave of pipe, wherein, EG is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the magnesium acetate four water salt of 700 weight ppm again, 250 DEG C, with the condition of absolute manometer 101kPa under remove the methyl alcohol of by-product, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the tetrabutyl titanate ester catalyst of 150 weight ppm and the triethyl phosphate of 320 weight ppm, 280 DEG C, carry out 8 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, water-cooled limit, limit carries out cutting and making particle, obtains PET system resin (GF101X) of AV value 49 equivalents/ton, inherent viscosity 0.67.

(4) manufacture of PET resin (RF553C)

DMT49.8kg and EG33.1kg is joined and possesses mixer and distillate in the stainless steel autoclave of pipe, wherein, EG is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the magnesium acetate four water salt of 300 weight ppm again, 250 DEG C, with the condition of absolute manometer 101kPa under remove the methyl alcohol of by-product, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the tetrabutyl titanate ester catalyst of 50 weight ppm and the triethyl phosphate of 45 weight ppm, 280 DEG C, carry out 8 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, carry out cutting and making particle while carry out water-cooled limit.By obtained copolymer polyester resin particle under nitrogen atmosphere, at 100 DEG C after Pre-crystallizing 8 hours, in inertia stove (TABAI ESPEC Inc. INERT OVEN IPHH201), carry out 20 hours solid phase polycondensations at 215 DEG C under nitrogen circulation, obtain PET system resin (RF553C) of AV value 8 equivalents/ton, inherent viscosity 0.83.

(5) manufacture of PET resin (IS654)

In the same manner as the PET resin (IS654) used in the embodiment in mode (x) before, as described below manufacture to be made up of terephthalic acid (TPA) and M-phthalic acid and the PET resin that formed with the glycol component be made up of ethylene glycol of the dicarboxylic acid component of 30 % by mole that the copolymerization ratios of M-phthalic acid is dicarboxylic acid component's entirety.

DMT34.9kg, DMI14.9kg and EG35.4kg are joined and possesses mixer and distillate in the stainless steel autoclave of pipe, wherein, EG is that the mode making the mol ratio of glycol component and sour composition reach 2.2 is added, adding relative to obtained polyester is the calcium acetate of 300 weight ppm again, 250 DEG C, with the condition of absolute manometer 101kPa under remove the methyl alcohol of by-product, and carry out 5 hours ester exchange reactions.After ester exchange reaction terminates, adding relative to obtained polyester with the form of ethylene glycol solution is respectively the antimony trioxide catalyst of 240 weight ppm and the triethyl phosphate of 350 weight ppm, 280 DEG C, carry out 8 hours melt polycondensation reactions under the decompression of 66Pa after, extract out with strand form, water-cooled limit, limit carries out cutting and making particle, obtains PET system resin (IS654) of AV value 33 equivalents/ton, inherent viscosity 0.72.

< layer (B) forms material >

(1) manufacture of PVA system resin (B1-z)

Then, the concentration of copolymer is adjusted to 66% by the dilution of this solution with methanol, join in kneader, while solution temperature is remained on 40 DEG C, while carry out saponification with 2% methanol solution of the ratio relative to the total amount 1 mole of the vinyl acetate in copolymer and 3,4-diacetoxy-1-butylene being 12 mMs interpolation NaOH.While carrying out saponification saponified with graininess separate out and after becoming slurry, interpolation is the acetic acid of 1 equivalent relative to added amount of sodium hydroxide, adding methyl alcohol again makes the resin concentration in slurry reach 9%, stir 15 minutes in kneader, filter, after dispersion is stirred in methyl alcohol again, filter, dry in air drier, obtain PVA system resin (B1-z).

The saponification degree of PVA system resin (B1-z) obtained is with residual vinyl acetate and residual 3, the quantity of alkali consumption needed for hydrolysis of 4-diacetoxy-1-butylene is analyzed, result is 98.8 % by mole, and average degree of polymerization is analyzed according to JISK6726, and result is 450.In addition, the import volume of the side chain containing 1,2-dihydroxylic alcohols structure passes through ¹h-NMR spectrum (solvent: DMSO-d ₆, interior standard: tetramethylsilane) carry out measuring and calculating, result is 3 % by mole.In addition, namely the accessory substance of saponification is not 0.02 % by mole by the content of the sodium acetate utilizing the washing of methyl alcohol not remove.

(2) manufacture of PVA system resin (B2-z)

Then, the concentration of copolymer is adjusted to 66% by the dilution of this solution with methanol, join in kneader, while solution temperature is remained on 40 DEG C, while carry out saponification with 2% methanol solution of the ratio relative to the total amount 1 mole of the vinyl acetate in copolymer and 3,4-diacetoxy-1-butylene being 12 mMs interpolation NaOH.While carrying out saponification saponified with graininess separate out and after becoming slurry, interpolation is the acetic acid of 1 equivalent relative to added amount of sodium hydroxide, adding methyl alcohol again makes the resin concentration in slurry reach 9%, stir 15 minutes in kneader, filter, after dispersion is stirred in methyl alcohol again, filter, dry in air drier, obtain PVA system resin.

The saponification degree of PVA system resin (B2-z) obtained is with residual vinyl acetate and residual 3, the quantity of alkali consumption needed for hydrolysis of 4-diacetoxy-1-butylene is analyzed, result is 98.7 % by mole, and average degree of polymerization is analyzed according to JISK6726, and result is 450.In addition, the import volume of the side chain containing 1,2-dihydroxylic alcohols structure passes through ¹h-NMR spectrum (solvent: DMSO-d ₆, interior standard: tetramethylsilane) carry out measuring and calculating, result is 6 % by mole.In addition, the content of sodium acetate is 0.02 % by mole.

(3) manufacture of PVA system resin (B3-z)

According to the compounding sodium acetate of amount (NaAc) relative to its entire infrastructure unit being 0.17 % by mole in PVA system resin (B2-z), use double screw extruder (TECHNOVEL CORPORATION KZW-15-60MG, screw diameter 15mm, L/D=60), at resin temperature 210 DEG C, melting mixing is carried out to it, obtain granular PVA system resin (B3-z).

(4) manufacture of PVA system resin (B4-z)

According to the compounding magnesium acetate of the amount (Mg (Ac) being respectively 0.039 % by mole, 0.17 % by mole relative to its entire infrastructure unit in PVA system resin (B2-z) ₂), sodium acetate (NaAc), use double screw extruder (TECHNOVEL CORPORATION KZW-15-60MG, screw diameter 15mm, L/D=60), at resin temperature 210 DEG C, melting mixing is carried out to it, obtain granular PVA system resin (B4-z).

(embodiment 14)

The 3-tier architecture body > that < is made up of layer (A) and layer (B)

Material is formed as the layer (A) shown in following, use above-mentioned PET system resin (MMA15), material is formed as layer (B), use above-mentioned PVA system resin (B1-z), utilize there is the T mould of 2 kinds 3 layers melt extrude forming machine, made the duplexer (film-form) (gross thickness 100 μm) of the 3-tier architecture be made up of layer (A)/layer (B)/layer (A) of the thickness 40 μm of thickness 20 μm, layer (A) of thickness 40 μm, layer (B) of layer (A).

< peel resistance (T stripping) >

In the same manner as the embodiment in mode (x) before, (y), use the 3-tier architecture body (film) obtained, measure the peel strength of layer (A) and layer (B) under the following conditions.Show the result in following table 4.

Sample: 15mm is wide, 200mm is long

Device: Shimadzu Corporation Autograph AG-100

Assay method: T stripping method (n=5)

Peeling rate: 100mm/min

(embodiment 15 ~ 17, comparative example 6 ~ 7)

Form material and PET system resin and layer (B) as the layer (A) in embodiment 14 and form material and PVA system resin, use the resin shown in following table 4, manufacture 3-tier architecture body similarly to Example 14 in addition, similarly evaluate.The results are shown in following table 4.

Table 4

< mode [z] >

※ 2 is equivalent to end carboxy concentration (mole/ton).

From the above results, the adhesiveness between layers of all embodiments is all excellent.Particularly employ in layer (A) and there is M-phthalic acid as employing the formation material being added with alkali metal salt and alkali salt (magnesium acetate, sodium acetate) in PVA system resin in the embodiment 16 of the PET series resin of copolymer composition and layer (B) and in the embodiment 17 obtained, adhesiveness between layers is excellent especially.

On the other hand, comparative example 6,7, due to the PET resin using end carboxy concentration too low, so the carboxyl becoming reaction site is few, does not therefore cause the sufficient esterification with glycol component, do not obtain the raising effect of cementability, thus result to be adhesiveness between layers poor.

In the above-described embodiments, show the concrete mode in the present invention, but above-described embodiment is only illustrate, and explains in non-limiting manner.And then, belong to the change of the equivalents of claims all within the scope of the invention.

utilizability in industry

Multilayer structure making of the present invention such as may be used for various packaging material, the various shape of containers such as packaging material for food, pharmaceuticals packaging material, industrial drug packing material, pesticides packaging material and becomes in the purposes of material.

Claims

1. a multilayer structure making, it is characterized in that, it is the multilayer structure making with the Rotating fields that layer (A) is laminated with layer (B), described layer (A) is containing by having PET series resin that dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component formed as main component, described layer (B) adjoins with above-mentioned layer (A), and containing there is the water-soluble polyvinyl alcohol resin of the construction unit shown in following general formula (1) as main component, above-mentioned layer (A) possesses any one in following manner (x) ~ (z) with the relation of layer (B),

[chemical formula 1]

In above-mentioned formula (1), R ¹, R ²and R ³separately represent hydrogen atom or organic group, X represents singly-bound or bonding chain, R ⁴, R ⁵and R ⁶separately represent hydrogen atom or organic group,

(x) layer (A) to be formed and the copolymerization ratios of dicarboxylic acids beyond terephthalic acid (TPA) in above-mentioned dicarboxylic acid component is the layer of PET series resin as main component of 15 ~ 40 % by mole of whole dicarboxylic acid component containing by having dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component, and layer (B) is the layer of water-soluble polyvinyl alcohol resin as main component containing having the construction unit shown in above-mentioned general formula (1);

(y) layer (A) is containing by having dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component is formed, and the copolymerization ratios of dicarboxylic acids beyond terephthalic acid (TPA) in above-mentioned dicarboxylic acid component is more than 2 % by mole of whole dicarboxylic acid component and lower than the PET series resin of 15 % by mole as the layer of main component, layer (B) be there is the construction unit shown in above-mentioned general formula (1) water-soluble polyvinyl alcohol resin as main component, also containing the layer relative to the entire infrastructure unit of above-mentioned water-soluble polyvinyl alcohol resin being at least one in the alkali metal salt of 0.03 ~ 1 % by mole and alkali salt,

(z) layer (A) to be formed and end carboxy concentration is the layer of PET series resin as main component of the scope of 15 ~ 60 equivalents/ton containing by having dicarboxylic acid component's unit of terephthalic acid (TPA) and the glycol component unit using ethylene glycol as main component, and above-mentioned layer (B) is the layer of water-soluble polyvinyl alcohol resin as main component containing having the construction unit shown in above-mentioned general formula (1).

2. multilayer structure making according to claim 1, in mode (x), containing water-soluble polyvinyl alcohol resin as in the layer (B) of main component, containing relative to the entire infrastructure unit of water-soluble polyvinyl alcohol resin being at least one in the alkali metal salt of 0.001 ~ 1 % by mole and alkali salt.

3. multilayer structure making according to claim 1, in mode (z), above-mentioned PET series resin has the PET series resin that terephthalic acid (TPA) is the scope of 2 ~ 40 % by mole of whole dicarboxylic acid component as dicarboxylic acid component, the copolymerization ratios of dicarboxylic acids that has beyond the terephthalic acid (TPA) of ethylene glycol as the main component of glycol component and in dicarboxylic acid component.

4. the multilayer structure making according to claim 1 or 3, in mode (z), containing water-soluble polyvinyl alcohol resin as in the layer (B) of main component, containing relative to the entire infrastructure unit of water-soluble polyvinyl alcohol resin being at least one in the alkali metal salt of 0.001 ~ 1 % by mole and alkali salt.

5. the multilayer structure making according to any one of claims 1 to 3, wherein, the dicarboxylic acids beyond above-mentioned terephthalic acid (TPA) is M-phthalic acid.